Phosphorus bridged metallocene compounds for olefin polymerization

ABSTRACT

This invention relates to metallocene compounds represented by formula:  
                 
wherein M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide metal atom, or actinide metal atom; E is a substituted or unsubstituted indenyl ligand that is bonded to Y through the two position of the indenyl ring; A is bonded to Y, and is a substituted or unsubstituted cyclopentadienyl ligand, a substituted or unsubstituted heterocyclopentadienyl ligand, a substituted or unsubstituted indenyl ligand, a substituted or unsubstituted heteroindenyl ligand, a substituted or unsubstituted fluorenyl ligand, a substituted or unsubstituted heterofluorenyl ligand, or other mono-anionic ligand, or A may, independently, be defined as E; Y is a phosphorus containing group that is bonded to both E and A, and is bonded via the phosphorus atom to E; and X are, independently, univalent anionic ligands, or both X are joined and bound to the metal atom to form a metallocycle ring, or both X join to form a chelating ligand, a diene ligand, or an alkylidene ligand.

This application claims the benefit of U.S. application No. 60/564,907filed Apr. 23, 2004.

FIELD

A series of novel phosphorus bridged transition metal compounds havebeen synthesized, and when activated, have been shown to be useful asolefin polymerization catalysts.

BACKGROUND

Various processes and catalysts exist for the homopolymerization orcopolymerization of olefins. For many applications, it is desirable fora polyolefin to have a high weight average molecular weight while havinga relatively narrow molecular weight distribution. A high weight averagemolecular weight, when accompanied by a narrow molecular weightdistribution, provides a polyolefin with, among other things, highstrength properties.

Traditional Ziegler-Natta catalysts systems—a transition metal compoundco-catalyzed by an aluminum alkyl—are typically capable of producingpolyolefins having a high molecular weight, but with a broad molecularweight distribution.

More recently a catalyst system has been developed wherein thetransition metal compound has two or more cyclopentadienyl ringligands—such transition metal compound being referred to herein as a“metallocene—which catalyzes the production of olefin monomers topolyolefins. Accordingly, titanocenes, zirconocenes and hafnocenes, havebeen utilized as the transition metal component in such “metallocene”containing catalyst system for the production of polyolefins andethylene-alpha-olefin copolymers.

Organometallics 1998, 17, 2155 discloses phosphorus bridgedbis-cyclopentadienyl ligands with four bonds to the phosphorus bridge.Group 4 metals are not used.

J. Mol. Cat. A. 1998, 128, 245 discloses phosphorus bridged ligands withthree bonds to the phosphorus ligand. Compounds includePhP(fluoreyl)(cyclopentadienyl)ZrCl₂, PhP(fluorenyl)₂ZrCl₂,1,1′-PhP(2-methyl-4-phenylindenyl)₂ZrCl₂ (bridged in the one position),1,1′-iso-propylP(PhP(2-methyl-4-phenylindenyl)₂ZrCl₂ (bridged in the oneposition), 1,1′-PhP(indenyl)₂ZrCl₂ (bridged in the one position).

J. Organomet. Chem. 1998, 568, 127 discloses phosphorus bridged ligandswith three bonds to the phosphorous ligand. Compounds includePhP(fluorenyl)₂ZrCl₂, and PhP(fluorenyl)₂HfCl₂. The paper also disclosessome additional ligand preps, but not with bridges in the 2-position ofthe indenyl ligand. Polymerization data is included.

Organometallics 1999, 18, 6 discloses phosphorous bridgedbis-cyclopentadienyl Group 4 metallocenes with three or four bonds tothe phosphorous ligand (e.g. Cp*₂PMe, Cp*2PMe(E) with S═O, S, Se). Thereis a note in the paper stating that the compounds are activepolymerization catalysts when activated by MAO.

Z. Naturforsch., B 1999, 54, 482 discloses phosphorous bridgedbis-cyclopentadienyl complexes.

Organometallics 2000, 19, 5155—Discloses phosphorous bridgedbis-cyclopentadienyl Group 4 metallocenes with 4 bonds to thephosphorous ligand (e.g. Cp*₂PMe₂). This makes the metallocene ionic asin [Me₂PCp*₂ZrCl₂]⁺[I]⁻. There is no mention of polymerization.

SUMMARY OF THE INVENTION

Therefore, in accordance with an aspect of the present invention, thereare provided metallocene compounds represented by formula (1):

wherein

-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom;-   E is a substituted or unsubstituted indenyl ligand that is bonded to    Y through the two position of the indenyl ring;-   A is bonded to Y, and is a substituted or unsubstituted    cyclopentadienyl ligand, a substituted or unsubstituted    heterocyclopentadienyl ligand, a substituted or unsubstituted    indenyl ligand, a substituted or unsubstituted heteroindenyl ligand,    a substituted or unsubstituted fluorenyl ligand, a substituted or    unsubstituted heterofluorenyl ligand, or other mono-anionic ligand,    or A may, independently, be defined as E;-   Y is a phosphorus containing group that is bonded to both E and A,    and is bonded via the phosphorus atom to E; and-   X are, independently, univalent anionic ligands, or both X are    joined and bound to the metal atom to form a metallocycle ring, or    both X join to form a chelating ligand, a diene ligand, or an    alkylidene ligand.

This invention further relates to a catalyst system comprised of theabove metallocenes combined with an activator and to a process topolymerize unsaturated monomers using such catalyst system.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹H NMR spectrum of compound 12 in CD₂Cl₂.

FIG. 2 is a representation of the molecular structure of compound 25.

FIG. 3 is a representation of the molecular structure of compound 27.

DEFINITIONS

As used herein, the numbering scheme for the Periodic Table Groups isthe new notation as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27(1985).

As used herein, Me is methyl, t-Bu and ^(t)Bu are tertiary butyl, s-Buand ^(s)Bu is sec-butyl, i-Bu and ^(i)Bu are isobutyl, iPr and ^(i)Prare isopropyl, Cy is cyclohexyl, and Ph is phenyl.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group”, “radical”, and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals, that may be linear, branched, or cyclic,and when cyclic, aromatic or non-aromatic, and include substitutedhydrocarbyl radicals, halocarbyl radicals, and substituted halocarbylradicals, silylcarbyl radicals, and germylcarbyl radicals as these termsare defined below. When referring to a hydrogen substitutent, the terms“hydrogen” and “hydrogen radical” are used interchangeably.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*3, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—,═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. Additionally, two or more R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR⁵ ₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical and two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Polar radicals or polar groups are groups in which the heteroatomfunctionality is bonded directly to the indicated atom or atoms. Theyinclude heteroatoms of groups 1-17 of the periodic table either alone orconnected to other elements by covalent or other interactions such asionic, van der Waals forces, or hydrogen bonding. Examples of functionalgroups include carboxylic acid, acid halide, carboxylic ester,carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen(Group 14) analogues, alcohol and phenol, ether, peroxide andhydroperoxide, carboxylic amide, hydrazide and imide, amidine and othernitrogen analogues of amides, nitrile, amine and imine, azo, nitro,other nitrogen compounds, sulfur acids, selenium acids, thiols,sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphoruscompounds, silanes, boranes, borates, alanes, aluminates. Functionalgroups may also be taken broadly to include organic polymer supports orinorganic support material such as alumina, and silica. . Preferredexamples of polar groups include NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and the like where R* is independently ahydrocarbyl, substituted hydrocarbyl, halocarbyl or substitutedhalocarbyl radical as defined above and two R* may join together to forma substituted or unsubstituted saturated, partially unsaturated oraromatic cyclic or polycyclic ring structure.

In using the terms “substituted or unsubstituted cyclopentadienylligand”, “substituted or unsubstituted heterocyclopentadienyl ligand”,“substituted or unsubstituted indenyl ligand”, “substituted orunsubstituted heteroindenyl ligand”, “substituted or unsubstitutedfluorenyl ligand”, “substituted or unsubstituted heterofluorenylligand”, “substituted or unsubstituted pentadienyl ligand”, “substitutedor unsubstituted allyl ligand”, and “substituted or unsubstitutedboratabenzene ligand”, the substitution to the aforementioned ligand maybe hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, or germylcarbyl.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, triacontynyl, butadienyl,pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, anddecadienyl. Also included are isomers of saturated, partiallyunsaturated and aromatic cyclic and polycyclic structures wherein theradical may additionally be subjected to the types of substitutionsdescribed above. Examples include phenyl, methylphenyl, dimethylphenyl,ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl,methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl,norbornyl, norbornenyl, adamantyl and the like. For this disclosure,when a radical is listed, it indicates that radical type and all otherradicals formed when that radical type is subjected to the substitutionsdefined above. Alkyl, alkenyl and alkynyl radicals listed include allisomers including where appropriate cyclic isomers, for example, butylincludes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, andcyclobutyl (and analogous substituted cyclopropyls); pentyl includesn-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, and neopentyl (and analogous substituted cyclobutyls andcyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyland 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

For nomenclature purposes, the following numbering schemes are used forcyclopentadienyl, indenyl and fluorenyl rings. For cyclopentadienyldrawn below as an anionic ligand, all five numbered positions areequivalent. For indenyl also drawn below as an anionic ligand, positions1 and 3 are equivalent, 4 and 7 are equivalent, and 5 and 6 areequivalent. For fluorenyl drawn below as an anionic ligand, positions 1and 8 are equivalent, 2 and 7 are equivalent, 3 and 6 are equivalent,and 4 and 5 are equivalent.

A similar numbering and nomenclature scheme is used for heteroindenyland heterofluorenyl rings as illustrated below where Z and Qindependently represent the heteroatoms O, S, Se, or Te, or heteroatomgroups, NR′, PR′, AsR′, or SbR′ where R′ is hydrogen, or a hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,silylcarbyl, or germylcarbyl substituent. The number scheme shown belowis for heteroindenyl ligands or heterofluorenyl ligands that are bridgedto another ligand via a bridging group.

Examples include: Examples include: Cyclopenta[b]thienyl (Z═S)Cyclopenta[c]thienyl(Z═S) Cyclopenta[b]furanyl (Z═O)Cyclopenta[c]furanyl (Z═O) Cyclopenta[b]selenophenyl (Z═Se)Cyclopenta[c]selenophenyl (Z═Se) Cyclopenta[b]tellurophenyl (Z═Te)Cyclopenta[c]tellurophenyl (Z═Te) 6-Methyl-cyclopenta[b]pyrrolyl(Z═N—Me) 5-Methyl-cyclopenta[c]pyrrolyl (Z═N—Me)6-Methyl-cyclopenta[b]phospholyl (Z═P—Me)5-Methyl-cyclopenta[c]phospholyl (Z═P—Me) 6-Methyl-cyclopenta[b]arsolyl(Z═As—Me) 5-Methyl-cyclopenta[c]arsolyl (Z═As—Me)6-Methyl-cyclopenta[b]stibolyl (Z═Sb—Me) 5-Methyl-cyclopenta[c]stibolyl(Z═Sb—Me)

heterofluorenyl ligands

A similar numbering and nomenclature scheme is used forheterocyclopentadienyl rings as illustrated below where G and Jindependently represent the heteroatoms N, P, As, Sb or B. For theseligands when bridged to another ligand via a bridging group, the oneposition is usually chosen to be the ring carbon position where theligand is bonded to the bridging group, hence a numbering scheme is notillustrated below.

Examples include: Azacyclopentadiene (G═N) Phosphacyclopentadiene (G═P)Stibacyclopentadiene (G═Sb) Arsacyclopentadiene (G═As)Boracyclopentadiene (G═B)

Depending on the position of the bridging ligand, the numbering for thefollowing ligands will change; 1,3 and 1,2 are only used in this case toillustrate the position of the heteroatoms relative to one another.

Examples include: Examples include: 1,3-Diazacyclopentadiene (G═J═N)1,2-Diazacyclopentadiene (G═J═N) 1,3-Diphosphacyclopentadiene (G═J═P)1,2-Diphosphacyclopentadiene (G═J═P) 1,3-Distibacyclopentadiene (G═J═Sb)1,2-Distibacyclopentadiene (G═J═Sb) 1,3-Diarsacyclopentadiene (G═J═As)1,2-Diarsacyclopentadiene (G═J═As) 1,3-Dibomcyclopentadiene (G═J═B)1,2-Diboracyclopentadiene (G═J═B) 1,3-Azaphosphacyclopentadiene (G═N;J═P) 1,2-Azaphosphacyclopentadiene (G═N; J═P)1,3-Azastibacyclopentadiene (G═N; J═Sb) 1,2-Azastibacyclopentadiene(G═N; J═Sb) 1,3-Azarsacyclopentadiene (G═N; J═As)1,2-Azarsacyclopentadiene (G═N; J═As) 1,3-Azaboracyclopentadiene (G═N;J═B) 1,2-Azaboracyclopentadiene (G═N; J═B)1,3-Arsaphosphacyclopentadiene (G═As; J═P)1,2-Arsaphosphacyclopentadiene (G═As; J═P) 1,3-Arsastibacyclopentadiene(G═As; J═Sb) 1,2-Arsastibacyclopentadiene (G═As; J═Sb)1,3-Arsaboracyclopentadiene (G═As; J═B) 1,2-Arsaboracyclopentadiene(G═As; J═B) 1,3-Boraphosphacyclopentadiene (G═B; J═P)1,2-Boraphosphacyclopentadiene (G═B; J═P) 1,3-Borastibacyclopentadiene(G═B; J═Sb) 1,2-Borastibacyclopentadiene (G═B; J═Sb)1,3-Phosphastibacyclopentadiene (G═P; J═Sb)1,2-Phosphastibacyclopentadiene (G═P═J═Sb)

A “ring heteroatom” is a heteroatom that is within a cyclic ringstructure. A “heteroatom substituent” is heteroatom containing groupthat is directly bonded to a ring structure through the heteroatom. A“bridging heteroatom substituent” is a heteroatom or heteroatom groupthat is directly bonded to two different ring structures through theheteroatom. The terms “ring heteroatom”, “heteroatom substituent”, and“bridging heteroatom substituent” are illustrated below where Z and R′are as defined above. It should be noted that a “heteroatom substituent”can be a “bridging heteroatom substituent” when R′ is additionallydefined as the ligand “A”.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, an indenyl ligand has nine ring carbonatoms.

A “bondable ring position” is a ring position that is capable of bearinga substituent or bridging substituent. For example, cyclopenta[b]thienylhas five bondable ring positions (at the carbon atoms) and onenon-bondable ring position (the sulfur atom); cyclopenta[b]pyrrolyl hassix bondable ring positions (at the carbon atoms and at the nitrogenatom).

In the context of this document, “homopolymerization” would produce apolymer made from one monomer. For example, homopolymerization ofpropylene would produce homopolypropylene. Homopolymerization ofethylene would produce homopolyethylene. Likewise, “copolymerization”would produce polymers with more than one monomer type. For example,ethylene copolymers include polymers of ethylene with α-olefins, cyclicolefins and diolefins, vinylaromatic olefins, α-olefinic diolefins,substituted α-olefins, and/or acetylenically unsaturated monomers.Non-limiting examples of α-olefins include propylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene,1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene,1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane. Non-limiting examples of vinylaromatic olefinsinclude styrene, para-methylstyrene, para-t-butylstyrene,vinylnaphthylene, vinyltoluene, and divinylbenzene. Non-limitingexamples of α-olefinic dienes include 1,4-hexadiene, 1,5-hexadiene,1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene, 1,7-octadiene,7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene, 1,13-tetradeceneand 9-methyl-1,9-decadiene. Substituted α-olefins (also calledfunctional group containing α-olefins) include those containing at leastone non-carbon Group 13 to 17 atom bound to a carbon atom of thesubstituted α-olefin where such substitution if silicon may be adjacentto the double bond or terminal to the double bond, or anywhere inbetween, and where inclusion of non-carbon and non-silicon atoms such asfor example B, O, S, Se, Te, N, P, Ge, Sn, Pb, As, F, Cl, Br, or I, arecontemplated, where such non-carbon or non-silicon moieties aresufficiently far removed from the double bond so as not to interferewith the coordination polymerization reaction with the catalyst and soto retain the generally hydrocarbyl characteristic. By sufficiently farremoved from the double bond we intend that the number of carbon atoms,or the number of carbon and silicon atoms, separating the double bondand the non-carbon or non-silicon moiety may be 6 or greater, e.g. 7, or8, or 9, or 10, or 11, or 12, or 13, or 14 or more. The number of suchcarbon atoms, or carbon and silicon atoms, is counted from immediatelyadjacent to the double bond to immediately adjacent to the non-carbon ornon-silicon moiety. Examples include allyltrimethylsilane,divinylsilane, 8,8,8-trifluoro-1-octene, 8-methoxyoct-1-ene,8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene, or combinationsthereof. The use of functional group-containing α-olefins where thefunctional group is closer to the double bond is also within the scopeof embodiments of the invention when such olefins may be incorporated inthe same manner as are their α-olefin analogs. See, “MetalloceneCatalysts and Borane Reagents in The Block/Graft Reactions ofPolyolefins”, T. C. Chung, et al, Polym. Mater. Sci. Eng., v. 73, p. 463(1995), and the masked α-olefin monomers of U.S. Pat. No. 5,153,282.Such monomers permit the preparation of both functional-group containingcopolymers capable of subsequent derivatization, and of functionalmacromers which may be used as graft and block type polymeric segments.Copolymerization can also incorporate α-olefinic macromonomers of up to2000 mer units.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the olefin(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The term “catalyst system” is defined to mean a catalystprecursor/activator pair. When “catalyst system” is used to describesuch a pair before activation, it means the unactivated catalyst(precatalyst) together with an activator and, optionally, aco-activator. When it is used to describe such a pair after activation,it means the activated catalyst and the activator or othercharge-balancing moiety.

The transition metal compound may be neutral as in a precatalyst, or acharged species with a counter ion as in an activated catalyst system.

Catalyst precursor is also often referred to as precatalyst, catalyst,catalyst precursor and transition metal compound or complex. These wordsare used interchangeably. Activator and cocatalyst are also usedinterchangeably. A scavenger is a compound that is typically added tofacilitate oligomerization or polymerization by scavenging impurities.Some scavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Insome embodiments a co-activator can be pre-mixed with the transitionmetal compound to form an alkylated transition metal compound, alsoreferred to as an alkylated invention compound.

Noncoordinating anion (NCA) is defined to mean an anion either that doesnot coordinate to the catalyst metal cation or that does coordinate tothe metal cation, but only weakly. An NCA coordinates weakly enough thata neutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complex maybe used or contained in the noncoordinating anion. Suitable metalsinclude, but are not limited to, aluminum, gold, and platinum. Suitablemetalloids include, but are not limited to, boron, aluminum, phosphorus,and silicon.

A stoichiometric activator can be either neutral or ionic. The termsionic activator, and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activator,and Lewis acid activator can be used interchangeably.

DETAILED DESCRIPTION OF THE INVENTION

The metallocene compounds according to the invention can be used as acatalyst component for the production of homopolymers, such ashomopolyethylene or homopolypropylene, and for copolymers of ethylenewith other olefins including alpha-olefins or copolymers of propylenewith other olefins including alpha-olefins.

In a preferred embodiment this invention relates to transition metalcompounds represented by formula (2):

where:

-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, preferably a Group 4 transition    metal atom selected from titanium, zirconium or hafnium;-   each R¹, R², R³, R⁴, R⁵, and R⁶ is, independently, a hydrogen, or a    hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted    halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or    substituted germylcarbyl substituent, and optionally, adjacent R¹,    R², R³, R⁴, R⁵, and R⁶ groups may join together to form a    substituted or unsubstituted, saturated, partially unsaturated, or    aromatic cyclic or polycyclic substituent;-   A is a substituted or unsubstituted cyclopentadienyl ligand, a    substituted or unsubstituted heterocyclopentadienyl ligand, a    substituted or unsubstituted indenyl ligand, a substituted or    unsubstituted heteroindenyl ligand, a substituted or unsubstituted    fluorenyl ligand, or a substituted or unsubstituted heterofluorenyl    ligand where A is bonded to Y through any bondable ring position; or    A is a mono-anionic ligand such as a substituted or unsubstituted    pentadienyl ligand, a substituted or unsubstituted allyl ligand, or    a substituted or unsubstituted boratabenzene ligand; and-   Y is PR, RP—PR, or RN—PR, where each R is, independently, a    hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted    halocarbyl substituent, and optionally, adjacent R groups may join    together to form a substituted or unsubstituted, saturated or    partially unsaturated cyclic or polycyclic substituent;-   X are, independently, hydride radicals, hydrocarbyl radicals,    substituted hydrocarbyl radicals, halocarbyl radicals, substituted    halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl    radicals, germylcarbyl radicals, or substituted germylcarbyl    radicals; or both X are joined and bound to the metal atom to form a    metallacycle ring containing from about 3 to about 20 carbon atoms;    or both together can be an olefin, diolefin or aryne ligand; or both    X may, independently, be a halogen, alkoxide, aryloxide, amide,    phosphide or other univalent anionic ligand or both X can also be    joined to form a anionic chelating ligand.

More preferably this invention relates to compounds represented byformula (3):

where:

-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, preferably a Group 4 transition    metal atom selected from titanium, zirconium or hafnium;-   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is,    independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl,    halocarbyl, substituted halocarbyl, silylcarbyl, substituted    silylcarbyl, germylcarbyl, or substituted germylcarbyl substituent,    and optionally, adjacent R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,    R¹¹, and R¹² substituents may join together to form a substituted or    unsubstituted, saturated, partially unsaturated, or aromatic cyclic    or polycyclic substituent; and-   Y is PR, RP—PR, or RN—PR, where each R is, independently, a    hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted    halocarbyl substituent, and optionally, adjacent R groups may join    together to form a substituted or unsubstituted, saturated or    partially unsaturated cyclic or polycyclic substituent;-   X are, independently, hydride radicals, hydrocarbyl radicals,    substituted hydrocarbyl radicals, halocarbyl radicals, substituted    halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl    radicals, germylcarbyl radicals, or substituted germylcarbyl    radicals; or both X are joined and bound to the metal atom to form a    metallacycle ring containing from about 3 to about 20 carbon atoms;    or both together can be an olefin, diolefin or aryne ligand; or each    X may, independently, be a halogen, alkoxide, aryloxide, amide,    phosphide or other univalent anionic ligand or both X can also be    joined to form a anionic chelating ligand.

Examples of specific preferred embodiments are tabulated below in Table1, where some representative components are listed. Not listed, is Mwhich is defined above; M is, preferably, titanium, zirconium, orhafnium. When alkyl, alkenyl and alkynyl radicals are disclosed in thisapplication the term includes all isomers and all substitution types, aspreviously described, unless otherwise stated. Listings for the ligand“A” include all bondable ring positions and all possible isomers. Forexample, a listing under “A” of indenyl would include 1-indenyl,2-indenyl, 4-indenyl and 5-indenyl where the number indicates thebridging position; a listing of methylindenyl would include2-(1-methylindenyl), 3-(1-methylindenyl), 4-(1-methylindenyl),5-(1-methylindenyl), 6-(1-methylindenyl), 7-(1-methylindenyl),1-(2-methylindenyl), 4-(2-methylindenyl), 5-(2-methylindenyl),1-(4-methylindenyl), 2-(4-methylindenyl), 3-(4-methylindenyl),5-(4-methylindenyl), 6-(4-methylindenyl), 7-(4-methylindenyl),1-(5-methylindenyl), 2-(5-methylindenyl), 3-(5-methylindenyl),4-(5-methylindenyl), 6-(5-methylindenyl), and 7-(5-methylindenyl) wherethe number outside the parenthesis indicates the bridging position. Whenmore than one substituent is listed, for example, propylphenylindenyl,propyl and phenyl are each substituents on the indenyl ring, as comparedto (propylphenyl)indenyl where propyl is a substituent on the phenylring which in turn is a substituent on the indenyl ring. The columnlabeled “R” shows some examples of substituents that can serve as R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹². The selection of onesubstituent is independent of the selection any other substituent. Inother words, the invention allows R¹═R²═R³═R⁴═R⁵═R⁶═R⁷═R⁸═R⁹═R¹⁰═R¹¹═R¹²but does not demand it. Likewise, each X may be chosen independently ofone another. To illustrate members of the transition metal component,select a transition metal, and select any combination of the specieslisted in Table 1 for a given formula illustrated above. For example,using formula 2, zirconium as the transition metal, and thesubstituents/ligands in the first row of Table 1, the compound2,2′-methylphosphindiyl(cyclopenta[b]thienyl)(indenyl)zirconiumdihydride is illustrated. Any combination of components may be selectedusing the above formulae 2 or 3, and any Group 3, 4, 5 or 6 transitionmetal atom (preferably Ti, Zr or Hf). While Table 1 does not specify thebridging position of the ligand Y, formula 2 limits it to a bridge inthe two position of a substituted or unsubstituted indenyl ligand, andto any possible bridging position of the ligand A—for example, thecompound 2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconiumdichloride, where the methylphosphindiyl bridging ligand is bonded tothe 2 position of the indenyl ligand and to the 1 position of thecyclopentadienyl ligand. Formula 3 further limits the bonding of thebridging ligand to the two position of each substituted or unsubstitutedindenyl ligand—for example, the compound2,2′-cyclohexylphosphindiyl-bis(indenyl)zirconium dichloride, where the2 and 2′ indicate the cyclohexylphosphindiyl bridge is bonded to the2-position of each of the indenyl ligands. When two different ligandsare being bridged by a phosphindiyl ligand, the first number representsthe position the bridge is bonded to the first ligand and the secondnumber (typically a number followed by an′) represents the position thebridge is bonded to the second ligand.

Additional examples illustrated by Table 1 would include:

-   2,2′-phenylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-cyclopropylphosphindiyl(1-methylindenyl)(tetramethylcyclopentadienyl)zirconium    dichloride,-   2,1′-cyclobutylphosphindiyl-bis(indenyl)zirconium methyl chloride-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dimethyl,-   2,2′-(1,2-diphenyldiphosphandiyl)-bis(indenyl)titanium difluoride,

2,2′-(1-methyl-2-phenyldiphosphandiyl)-bis(indenyl)zirconiummethylidene, and the like. TABLE 1 R¹, R², R³, R⁴, R⁵, R⁶, R⁷, Y A R⁸,R⁹, R¹⁰, R¹¹, or R¹² X methylphosphindiyl cyclopenta[b]thienyl hydrogenhydride ethylphosphindiyl cyclopenta[b]furanyl methyl fluoridepropylphosphindiyl cyclopenta[b]selenophenyl ethyl chloridebutylphosphindiyl cyclopenta[b]tellurophenyl propyl bromidepentylphosphindiyl cyclopenta[b]pyrrolyl butyl iodide hexylphosphindiylcyclopenta[b]phospholyl pentyl methyl heptylphosphindiylcyclopenta[b]arsolyl hexyl ethyl octylphosphindiyl cyclopenta[b]stibolylheptyl propyl nonylphosphindiyl methylcyclopenta[b]thienyl octyl butyldecylphosphindiyl methylcyclopenta[b]furanyl nonyl pentylundecylphosphindiyl methylcyclopenta[b]selenophenyl decyl hexyldodecylphosphindiyl methylcyclopenta[b]tellurophenyl undecyl heptyltridecylphosphindiyl methylcyclopenta[b]pyrrolyl dodecyl octyltetradecylphosphindiyl methylcyclopenta[b]phospholyl tridecyl nonylpentadecylphosphindiyl methylcyclopenta[b]arsolyl tetradecyl decylhexadecylphosphindiyl methylcyclopenta[b]stibolyl pentadecyl undecylheptadecylphosphindiyl dimethylcyclopenta[b]thienyl hexadecyl dodecyloctadecylphosphindiyl dimethylcyclopenta[b]furanyl heptadecyl tridecylnonadecylphosphindiyl dimethylcyclopenta[b]pyrrolyl octadecyl tetradecyleicosylphosphindiyl dimethylcyclopenta[b]phospholyl nonadecyl pentadecylheneicosylphosphindiyl trimethylcyclopenta[b]thienyl eicosyl hexadecyldocosylphosphindiyl trimethylcyclopenta[b]furanyl heneicosyl heptadecyltricosylphosphindiyl trimethylcyclopenta[b]pyrrolyl docosyl octadecyltetracosylphosphindiyl trimethylcyclopenta[b]phospholyl tricosylnonadecyl pentacosylphosphindiyl tetramethylcyclopenta[b]pyrrolyltetracosyl eicosyl hexacosylphosphindiyltetramethylcyclopenta[b]phospholyl pentacosyl heneicosylheptacosylphosphindiyl ethylcyclopenta[b]thienyl hexacosyl docosyloctacosylphosphindiyl ethylcyclopenta[b]furanyl heptacosyl tricosylnonacosylphosphindiyl ethylcyclopenta[b]pyrrolyl octacosyl tetracosyltriacontylphosphindiyl ethylcyclopenta[b]phospholyl nonacosyl pentacosylvinylphosphindiyl diethylcyclopenta[b]thienyl triacontyl hexacosylpropenylphosphindiyl diethylcyclopenta[b]furanyl vinyl heptacosylbutenylphosphindiyl diethylcyclopenta[b]pyrrolyl propenyl octacosylpentenylphosphindiyl diethylcyclopenta[b]phospholyl butenyl nonacosylhexenylphosphindiyl triethylcyclopenta[b]thienyl pentenyl triacontylheptenylphosphindiyl triethylcyclopenta[b]furanyl hexenyl vinyloctenylphosphindiyl triethylcyclopenta[b]pyrrolyl heptenyl propenylnonenylphosphindiyl triethylcyclopenta[b]phospholyl octenyl butenyldecenylphosphindiyl propylcyclopenta[b]thienyl nonenyl pentenylundecenylphosphindiyl propylcyclopenta[b]furanyl decenyl hexenyldodecenylphosphindiyl propylcyclopenta[b]pyrrolyl undecenyl heptenyltridecenylphosphindiyl propylcyclopenta[b]phospholyl dodecenyl octenyltetradecenylphosphindiyl dipropylcyclopenta[b]thienyl tridecenyl nonenylpentadecenylphosphindiyl dipropylcyclopenta[b]furanyl tetradecenyldecenyl hexadecenylphosphindiyl dipropylcyclopenta[b]pyrrolylpentadecenyl undecenyl heptadecenylphosphindiyldipropylcyclopenta[b]phospholyl hexadecenyl dodecenyloctadecenylphosphindiyl tripropylcyclopenta[b]thienyl heptadecenyltridecenyl nonadecenylphosphindiyl tripropylcyclopenta[b]furanyloctadecenyl tetradecenyl eicosenylphosphindiyltripropylcyclopenta[b]pyrrolyl nonadecenyl pentadecenylheneicosenylphosphindiyl tripropylcyclopenta[b]phospholyl eicosenylhexadecenyl docosenylphosphindiyl butylcyclopenta[b]thienyl heneicosenylheptadecenyl tricosenylphosphindiyl butylcyclopenta[b]furanyl docosenyloctadecenyl tetracosenylphosphindiyl butylcyclopenta[b]pyrrolyltricosenyl nonadecenyl pentacosenylphosphindiylbutylcyclopenta[b]phospholyl tetracosenyl eicosenylhexacosenylphosphindiyl dibutylcyclopenta[b]thienyl pentacosenylheneicosenyl heptacosenylphosphindiyl dibutylcyclopenta[b]furanylhexacosenyl docosenyl octacosenylphosphindiyldibutylcyclopenta[b]pyrrolyl heptacosenyl tricosenylnonacosenylphosphindiyl dibutylcyclopenta[b]phospholyl octacosenyltetracosenyl triacontenylphosphindiyl tributylcyclopenta[b]thienylnonacosenyl pentacosenyl propynylphosphindiyltributylcyclopenta[b]furanyl triacontenyl hexacosenylbutynylphosphindiyl tributylcyclopenta[b]pyrrolyl propynyl heptacosenylpentynylphosphindiyl tributylcyclopenta[b]phospholyl butynyl octacosenylhexynylphosphindiyl ethylmethylcyclopenta[b]thienyl pentynyl nonacosenylheptynylphosphindiyl ethylmethylcyclopenta[b]furanyl hexynyltriacontenyl octynylphosphindiyl ethylmethylcyclopenta[b]pyrrolylheptynyl propynyl nonynylphosphindiyl ethylmethylcyclopenta[b]phospholyloctynyl butynyl decynylphosphindiyl methylpropylcyclopenta[b]thienylnonynyl pentynyl undecynylphosphindiyl methylpropylcyclopenta[b]furanyldecynyl hexynyl dodecynylphosphindiyl methylpropylcyclopenta[b]pyrrolylundecynyl heptynyl tridecynylphosphindiylmethylpropylcyclopenta[b]phospholyl dodecynyl octynyltetradecynylphosphindiyl butylmethylcyclopenta[b]thienyl tridecynylnonynyl pentadecynylphosphindiyl butylmethylcyclopenta[b]furanyltetradecynyl decynyl hexadecynylphosphindiylbutylmethylcyclopenta[b]pyrrolyl pentadecynyl undecynylheptadecynylphosphindiyl butylmethylcyclopenta[b]phospholyl hexadecynyldodecynyl octadecynylphosphindiyl cyclopenta[c]thienyl heptadecynyltridecynyl nonadecynylphosphindiyl cyclopenta[c]furanyl octadecynyltetradecynyl eicosynylphosphindiyl cyclopenta[c]selenophenyl nonadecynylpentadecynyl heneicosynylphosphindiyl cyclopenta[c]tellurophenyleicosynyl hexadecynyl docosynylphosphindiyl cyclopenta[c]pyrrolylheneicosynyl heptadecynyl tridecynylphosphindiyl cyclopenta[c]phospholyldocosynyl octadecynyl tetradecynylphosphindiyl cyclopenta[c]arsolyltricosynyl nonadecynyl pentadecynylphosphindiyl cyclopenta[c]stibolyltetracosynyl eicosynyl hexadecynylphosphindiylmethylcyclopenta[c]thienyl pentacosynyl heneicosynylheptadecynylphosphindiyl methylcyclopenta[c]furanyl hexacosynyldocosynyl octadecynylphosphindiyl methylcyclopenta[c]selenophenylheptacosynyl tricosynyl nonadecynylphosphindiylmethylcyclopenta[c]tellurophenyl octacosynyl tetracosynyleicosynylphosphindiyl methylcyclopenta[c]pyrrolyl nonacosynylpentacosynyl heneicosynylphosphindiyl methylcyclopenta[c]phospholyltriacontynyl hexacosynyl docosynylphosphindiylmethylcyclopenta[c]arsolyl cyclopropyl heptacosynyltricosynylphosphindiyl methylcyclopenta[c]stibolyl cyclobutyloctacosynyl tetracosynylphosphindiyl dimethylcyclopenta[c]thienylcyclopentyl nonacosynyl pentacosynylphosphindiyldimethylcyclopenta[c]furanyl cyclohexyl triacontynylhexacosynylphosphindiyl dimethylcyclopenta[c]pyrrolyl cycloheptylcyclopropyl heptacosynylphosphindiyl dimethylcyclopenta[c]phospholylcyclooctyl cyclobutyl octacosynylphosphindiyltrimethylcyclopenta[c]thienyl cyclononyl cyclopentylnonacosynylphosphindiyl trimethylcyclopenta[c]furanyl cyclodecylcyclohexyl triacontynylphosphindiyl trimethylcyclopenta[c]pyrrolylcycloundecyl cycloheptyl cyclopropylphosphindiyltrimethylcyclopenta[c]phospholyl cyclododecyl cyclooctylcyclobutylphosphindiyl tetramethylcyclopenta[c]pyrrolyl cyclotetradecylcyclononyl cyclopentylphosphindiyl tetramethylcyclopenta[c]phospholylcyclopentenyl cyclodecyl cyclohexylphosphindiylethylcyclopenta[c]thienyl cyclohexenyl cycloundecylcycloheptylphosphindiyl ethylcyclopenta[c]furanyl cycloheptenylcyclododecyl cyclooctylphosphindiyl ethylcyclopenta[c]pyrrolylcyclooctenyl cyclotetradecyl cyclononylphosphindiylethylcyclopenta[c]phospholyl cyclodecenyl cyclopentenylcyclodecylphosphindiyl diethylcyclopenta[c]thienyl cyclododecenylcyclohexenyl cycloundecylphosphindiyl diethylcyclopenta[c]furanylmethylcyclohexyl cycloheptenyl cyclododecylphosphindiyldiethylcyclopenta[c]pyrrolyl ethylcyclohexyl cyclooctenylcyclotetradecylphosphindiyl diethylcyclopenta[c]phospholylpropylcyclohexyl cyclodecenyl cyclohexadecylphosphindiyltriethylcyclopenta[c]thienyl dimethylcyclohexyl cyclododecenylcyclooctadecylphosphindiyl triethylcyclopenta[c]furanyldiethylcyclohexyl methylcyclohexyl (methylcyclohexyl)phosphindiyltriethylcyclopenta[c]pyrrolyl dipropylcyclohexyl ethylcyclohexyl(ethylcyclohexyl)phosphindiyl triethylcyclopenta[c]phospholyl phenylpropylcyclohexyl (propylcyclohexyl)phosphindiylpropylcyclopenta[c]thienyl tolyl dimethylcyclohexyl(dimethylcyclohexyl)phosphindiyl propylcyclopenta[c]furanyl mesityldiethylcyclohexyl (diethylcyclohexyl)phosphindiylpropylcyclopenta[c]pyrrolyl ethylphenyl dipropylcyclohexyl(dipropylcyclohexyl)phosphindiyl propylcyclopenta[c]phospholylpropylphenyl phenyl phenylphosphindiyl dipropylcyclopenta[c]thienylbutylphenyl tolyl tolylphosphindiyl dipropylcyclopenta[c]furanylpentylphenyl mesityl mesitylphosphindiyl dipropylcyclopenta[c]pyrrolylhexylphenyl ethylphenyl (ethylphenyl)phosphindiyldipropylcyclopenta[c]phospholyl dimethylphenyl propylphenyl(propylphenyl)phosphindiyl tripropylcyclopenta[c]thienyl trimethylphenylbutylphenyl (butylphenyl)phosphindiyl tripropylcyclopenta[c]furanyldiethylphenyl pentylphenyl (pentylphenyl)phosphindiyltripropylcyclopenta[c]pyrrolyl diethylmethylphenyl hexylphenyl(hexylphenyl)phosphindiyl tripropylcyclopenta[c]phospholyldipropylphenyl dimethylphenyl dimethylphenyl)phosphindiylbutylcyclopenta[c]thienyl dipropylmethylphenyl trimethylphenyl(trimethylphenyl)phosphindiyl butylcyclopenta[c]furanyl benzyldiethylphenyl (diethylphenyl)phosphindiyl butylcyclopenta[c]pyrrolylphenethyl diethylmethylphenyl (diethylmethylphenyl)phosphindiylbutylcyclopenta[c]phospholyl napthyl dipropylphenyl(dipropylphenyl)phosphindiyl dibutylcyclopenta[c]thienyl norbornyldipropylmethylphenyl (dipropylmethylphenyl)phosphindiyldibutylcyclopenta[c]furanyl adamantyl benzyl biphenylphosphindiyldibutylcyclopenta[c]pyrrolyl trifluoromethyl phenethylphenethylphosphindiyl dibutylcyclopenta[c]phospholylmethyltrifluoromethyl napthyl napthylphosphindiyltributylcyclopenta[c]thienyl trimethylsilyl trifluoromethylnorbornylphosphindiyl tributylcyclopenta[c]furanyl trimethylgermylmethoxy adamantylphosphindiyl tributylcyclopenta[c]pyrrolyltrimethylsilylmethyl ethoxy fluoromethylphosphindiyltributylcyclopenta[c]phospholyl trimethylgermylmethyl propoxyfluoroethylphosphindiyl ethylmethylcyclopenta[c]thienyl methoxymethylbutoxy fluoropropylphosphindiyl ethylmethylcyclopenta[c]furanylethoxymethyl dimethylamido fluorobutylphosphindiylethylmethylcyclopenta[c]pyrrolyl propoxymethyl diethylamidofluoropentylphosphindiyl ethylmethylcyclopenta[c]phospholyl butoxymethylmethylethylamido fluorohexylphosphindiylmethylpropylcyclopenta[c]thienyl phenoxymethyl phenoxyfluoroheptylphosphindiyl methylpropylcyclopenta[c]furanyl methylsulfanylbenzoxy fluorooctylphosphindiyl methylpropylcyclopenta[c]pyrrolylethylsulfanyl allyl fluorononylphosphindiylmethylpropylcyclopenta[c]phospholyl propylsulfanyl 1,1-dimethyl allylfluorodecylphosphindiyl butylmethylcyclopenta[c]thienyl butylsulfanylacetylacetonate fluoroundecylphosphindiylbutylmethylcyclopenta[c]furanyl phenylsulfanyl 1,1,1,5,5,5-hexa-fluoroacetylacetonate fluorododecylphosphindiylbutylmethylcyclopenta[c]pyrrolyl dimethylaminomethyl 1,1,1-trifluoro-acetylacetonate thienylphosphindiyl butylmethylcyclopenta[c]phospholyldimethylaminoethyl 2-carboxymethyl allyl furanylphosphindiyl indenyldiphenylaminomethyl 1,1,1-trifluoro-5,5-di- methylacetylacetonatepyrrolylphosphindiyl methylindenyl diphenylaminoethyl methoxymethylphospholylphosphindiyl dimethylindenyl phenylaminomethyl ethoxymethyl(methylthienyl)phosphindiyl trimethylindenyl phenylaminoethylpropoxymethyl (methylfuranyl)phosphindiyl tetramethylindenylmethylaminomethyl butoxymethyl (methylpyrrolyl)phosphindiylpentamethylindenyl dimethylphosphinomethyl phenoxymethyl(methylphospholyl)phosphindiyl hexamethylindenyl dimethylphosphinoethylmethylsulfanyl (propylthienyl)phosphindiyl ethylindenyldiphenylphosphinomethyl ethylsulfanyl (propylfuranyl)phosphindiyldiethylindenyl phenylphosphinoethyl propylsulfanyl(propylpyrrolyl)phosphindiyl triethylindenyl methylphosphinomethylbutylsulfanyl (propylphospholyl)phosphindiyl propylindenyl methoxyphenylsulfanyl (butylthienyl)phosphindiyl dipropylindenyl ethoxydimethylaminomethyl (butylfuranyl)phosphindiyl tripropylindenyl propoxydimethylaminoethyl (butylpyrrolyl)phosphindiyl butylindenyl butoxydiphenylaminomethyl (butylphospholyl)phosphindiyl dibutylindenyldimethylamido phenylaminoethyl (pentylthienyl)phosphindiyltributylindenyl diethylamido phenylaminomethyl(pentylfuranyl)phosphindiyl pentylindenyl methylethylamidophenylaminoethyl (pentylpyrrolyl)phosphindiyl dipentylindenyl phenoxymethylaminomethyl (penylphospholyl)phosphindiyl tripentylindenyl benzoxydimethylphosphinomethyl (hexylthienyl)phosphindiyl hexylindenylmethylphenoxy dimethylphosphinoethyl (hexylfuranyl)phosphindiyldihexylindenyl ethylphenoxy diphenylphosphinomethyl(hexylpyrrolyl)phosphindiyl trihexylindenyl propylphenoxyphenylphosphinoethyl (hexylphospholyl)phosphindiyl heptylindenyldimethylphenoxy methylphosphinomethyl (heptylthienyl)phosphindiyloctylindenyl diethylphenoxy trimethylsilylmethyl(heptylfuranyl)phosphindiyl nonylindenyl dipropylphenoxytrimethylgermylmethyl (heptylpyrrolyl)phosphindiyl decylindenylmethylbenzoxy trimethylstannylmethyl (heptylphospholyl)phosphindiylphenylindenyl ethylbenzoxy fluoromethyl (octylthienyl)phosphindiylmethylphenylindenyl propylbenzoxy fluoroethyl (octylfuranyl)phosphindiylethylphenylindenyl dimethylbenzoxy fluoropropyl(octylpyrrolyl)phosphindiyl propylphenylindenyl diethylbenzoxyfluorobutyl (octylphospholyl)phosphindiyl butylphenylindenyldipropylbenzoxy fluoropentyl (nonylthienyl)phosphindiylpentylphenylindenyl perfluoroethyl fluorohexyl(nonylfuranyl)phosphindiyl hexylphenylindenyl perfluoropropylfluoroheptyl (nonylpyrrolyl)phosphindiyl heptylphenylindenylperfluorobutyl fluorooctyl (nonylphospholyl)phosphindiyloctylphenylindenyl perfluoropentyl fluorononyl(decylthienyl)phosphindiyl nonylphenylindenyl perfluorohexyl fluorodecyl(decylfuranyl)phosphindiyl decylphenylindenyl perfluoroheptylfluoroundecyl (decylpyrrolyl)phosphindiyl dimethylphenylindenylperfluorooctyl fluorododecyl (decylphospholyl)phosphindiyltrimethylphenylindenyl perfluorononyl fluorotridecyl(undecylthienyl)phosphindiyl dipropylphenylindenyl perfluorodecylfluorotetradecyl (undecylfuranyl)phosphindiyl methylpropylphenylindenylperfluoroundecyl fluoropentadecyl (undecylpyrrolyl)phosphindiyltolylindenyl perfluorododecyl fluorohexadecyl(undecylphospholyl)phosphindiyl methyltolylindenyl perfluorotridecylfluoroheptadecyl (dodecylthienyl)phosphindiyl ethyltolylindenylperfluorotetradecyl fluorooctadecyl (dodecylfuranyl)phosphindiylpropyltolylindenyl perfluoropentadecyl fluorononadecyl(dodecylpyrrolyl)phosphindiyl butyltolylindenyl perfluorohexadecylfluoroeicosyl (dodecylphospholyl)phosphindiyl pentyltolylindenylperfluoroheptadecyl fluorobenzyl (dimethylthienyl)phosphindiylhexyltolylindenyl perfluorooctadecyl difluorobenzyl(dimethylfuranyl)phosphindiyl heptyltolylindenyl perfluorononadecyltrifluorobenzyl (dimethylpyrrolyl)phosphindiyl octyltolylindenylperfluoroeicosyl tetrafluorobenzyl (dimethylphospholyl)phosphindiylnonyltolylindenyl fluoromethyl pentafluorobenzyl(diethylthienyl)phosphindiyl decyltolylindenyl fluoroethyltrifluoromethylbenzyl (diethylfuranyl)phosphindiyl dimethyltolylindenylfluoropropyl (diethylpyrrolyl)phosphindiyl trimethyltolylindenylfluorobutyl (diethylphospholyl)phosphindiyl dipropyltolylindenylfluoropentyl Both X (dipropylthienyl)phosphindiylmethylpropyltolylindenyl fluorohexyl methylidene(dipropylfuranyl)phosphindiyl naphthylindenyl fluoroheptyl ethylidene(dipropylpyrrolyl)phosphindiyl methylnaphthylindenyl fluorooctylpropylidene (dipropylphospholyl)phosphindiyl ethylnaphthylindenylfluorononyl tetramethylene (dibutylthienyl)phosphindiylpropylnaphthylindenyl fluorodecyl pentamethylene(dibutylfuranyl)phosphindiyl butylnaphthylindenyl fluoroundecylhexamethylene (dibutylpyrrolyl)phosphindiyl pentylnaphthylindenylfluorododecyl butadiene (dibutylphospholyl)phosphindiylhexylnaphthylindenyl fluorotridecyl methylbutadienefluorophenylphosphindiyl heptylnaphthylindenyl fluorotetradecyldimethylbutadiene difluorophenylphosphindiyl octylnaphthylindenylfluoropentadecyl pentadiene trifluorophenylphosphindiylnonylnaphthylindenyl fluorohexadecyl methylpentadienetetrafluorophenylphosphindiyl decylnaphthylindenyl fluoroheptadecyldimethylpentadiene pentafluorophenylphosphindiyl dimethylnaphthylindenylfluorooctadecyl hexadiene benzylphosphindiyl trimethylnaphthylindenylfluorononadecyl methylhexadiene trifluoromethylphosphindiyldipropylnaphthylindenyl fluoroeicosyl dimethylhexadienetrifluoromethylmethylphosphindiyl methylpropylnaphthylindenyl thienylpropandiyl perfluoroethylphosphindiyl (propylphenyl)indenyl fluranylbutandiyl perfluoropropylphosphindiyl methyl(propylphenyl)indenylpyrrolyl pentandiyl perfluorobutylphosphindiylethyl(propylphenyl)indenyl phospholyl hexandiylperfluoropentylphosphindiyl propyl(propylphenyl)indenyl methylthienylheptandiyl perfluorohexylphosphindiyl butyl(propylphenyl)indenylmethylfuranyl octandiyl perfluoroheptylphosphindiyldimethyl(propylphenyl)indenyl methylpyrrolyl nonandiylperfluorooctylphosphindiyl trimethyl(propylphenyl)indenylmethylphospholyl decandiyl perfluorononylphosphindiylmethylpropyl(propylphenyl)indenyl ethylthienyl dodecandiylperfluorodecylphosphindiyl (dipropylphenyl)indenyl ethylfuranyltetradecandiyl perfluoroundecylphosphindiylmethyl(dipropylphenyl)indenyl ethylpyrrolyl hexadecandiylperfluorododecylphosphindiyl ethyl(dipropylphenyl)indenylethylphospholyl octadecandiyl trimethylsilylmethylphosphindiylpropyl(dipropylphenyl)indenyl propylthienyl azapropandiyltrimethylgermylmethylphosphindiyl butyl(dipropylphenyl)indenylpropylfuranyl azabutandiyl methoxymethylphosphindiyldimethyl(dipropylphenyl)indenyl propylpyrrolyl azapentandiylethoxymethylphosphindiyl trimethyl(dipropylphenyl)indenylpropylphospholyl azahexandiyl propoxymethylphosphindiylmethylpropyl(dipropylphenyl)indenyl butylthienyl azaheptandiylbutoxymethylphosphindiyl (dimethylphenyl)indenyl butylfuranylazaoctandiyl phenoxymethylphosphindlyl methyl(dimethylphenyl)indenylbutylpyrrolyl azanonandiyl dimethylaminomethylphosphindiylethyl(dimethylphenyl)indenyl butylphospholyl azadecandiyldiphenylaminomethylphosphindiyl propyl(dimethylphenyl)indenylpentylthienyl azadodecandiyl diphenylphosphinomethylphosphindiylbutyl(dimethylphenyl)indenyl pentylfuranyl phosphapropandiylfluorobenzylphosphindiyl trimethyl(dimethylphenyl)indenyl pentylpyrrolylphosphabutandiyl difluorobenzylphosphindiyltrimethyl(dimethylphenyl)indenyl penylphospholyl phosphapentandiyltrifluorobenzylphosphindiyl methylpropyl(dimethylphenyl)indenylhexylthienyl thiapropandiyl tetrafluorobenzylphosphindiyl(trimethylphenyl)indenyl hexylfuranyl thiabutandiylpentafluorobenzylphosphindiyl methyl(trimethylphenyl)indenylhexylpyrrolyl thiapentandiyl trifluoromethylbenzylphosphindiylethyl(trimethylphenyl)indenyl hexylphospholyl catecholate1,2-dimethyldiphosphandiyl propyl(trimethylphenyl)indenyl heptylthienylbutylcatecholate 1,2-diethyldiphosphandiyl butyl(trimethylphenyl)indenylheptylfuranyl diazabutandiyl 1,2-dipropyldiphosphandiyldimethyl(trimethylphenyl)indenyl heptylpyrrolyl diazapentandiyl1,2-dibutyldiphosphandiyl trimethyl(trimethylphenyl)indenylheptylphospholyl diazahexandiyl 1,2-dipentyldiphosphandiylmethylpropyl(trimethylphenyl)indenyl octylthienyl dioxabutandiyl1,2-dihexyldiphosphandiyl trimethylsilylindenyl octylfuranyldioxapentandiyl 1,2-diheptyldiphosphandiyl trifluormethylindenyloctylpyrrolyl dioxahexandiyl 1,2-dioctyldiphosphandiyltrifluoromethylphenylindenyl octylphospholyl 1,2-dinonyldiphosphandiyl(benzothiopheneyl)indenyl nonylthienyl 1,2-didecyldiphosphandiyl(benzofuranyl)indenyl nonylfuranyl 1,2-diundecyldiphosphandiyl(fluorophenyl)indenyl nonylpyrrolyl 1,2-didodecyldiphosphandiyl(difluorophenyl)indenyl nonylphospholyl 1,2-ditridecyldiphosphandiyl(trifluorophenyl)indenyl decylthienyl 1,2-ditetradecyldiphosphandiyl(tetrafluorophenyl)indenyl decylfuranyl 1,2-dipentadecyldiphosphandiyl(pentafluorophenyl)indenyl decylpyrrolyl 1,2-dihexadecyldiphosphandiyl(trifluoromethylphenyl)indenyl decylphospholyl1,2-diheptadecyldiphosphandiyl (thienyl)indenyl undecylthienyl1,2-dioctadecyldiphosphandiyl (furanyl)indenyl undecylfuranyl1,2-dinonadecyldiphosphandiyl (pyrrolyl)indenyl undecylpyrrolyl1,2-dieicosyldiphosphandiyl (phospholyl)indenyl undecylphospholyl1,2-diheneicosyldiphosphandiyl (methylthienyl)indenyl dodecylthienyl1,2-didocosyldiphosphandiyl (methylfuranyl)indenyl dodecylfuranyl1,2-ditricosyldiphosphandiyl (methylpyrrolyl)indenyl dodecylpyrrolyl1,2-ditetracosyldiphosphandiyl (methylphospholyl)indenyldodecylphospholyl 1,2-dipentacosyldiphosphandiyl(dimethylthienyl)indenyl dimethylthienyl 1,2-dihexacosyldiphosphandiyl(dimethylfuranyl)indenyl dimethylfuranyl 1,2-diheptacosyldiphosphandiyl(dimethylpyrrolyl)indenyl dimethylpyrrolyl 1,2-dioctacosyldiphosphandiyl(dimethylphospholyl)indenyl dimethylphospholyl1,2-dinonacosyldiphosphandiyl (ethylthienyl)indenyl diethylthienyl1,2-ditriacontyldiphosphandiyl (ethylfuranyl)indenyl diethylfuranyl1,2-divinyldiphosphandiyl (ethylpyrrolyl)indenyl diethylpyrrolyl1,2-dipropenyldiphosphandiyl (ethylphospholyl)indenyl diethylphospholyl1,2-dibutenyldiphosphandiyl (propylthienyl)indenyl dipropylthienyl1,2-dipentenyldiphosphandiyl (propylfuranyl)indenyl dipropylfuranyl1,2-dihexenyldiphosphandiyl (propylpyrrolyl)indenyl dipropylpyrrolyl1,2-diheptenyldiphosphandiyl (propylphospholyl)indenyldipropylphospholyl 1,2-dioctenyldiphosphandiyl (butylthienyl)indenyldibutylthienyl 1,2-dinonenyldiphosphandiyl (butylfuranyl)indenyldibutylfuranyl 1,2-didecenyldiphosphandiyl (butylpyrrolyl)indenyldibutylpyrrolyl 1,2-diundecenyldiphosphandiyl (butylphospholyl)indenyldibutylphospholyl 1,2-didodecenyldiphosphandiylmethyl(benzothiopheneyl)indenyl dipentylthienyl1,2-dipropynyldiphosphandiyl methyl(benzofuranyl)indenyl dipentylfuranyl1,2-dibutynyldiphosphandiyl methyl(fluorophenyl)indenyl dipentylpyrrolyl1,2-dipentynyldiphosphandiyl methyl(difluorophenyl)indenyldipenylphospholyl 1,2-dihexynyldiphosphandiylmethyl(trifluorophenyl)indenyl dihexylthienyl1,2-diheptynyldiphosphandiyl methyl(tetrafluorophenyl)indenyldihexylfuranyl 1,2-dioctynyldiphosphandiylmethyl(pentafluorophenyl)indenyl dihexylpyrrolyl1,2-dinonynyldiphosphandiyl methyl(trifluoromethylphenyl)indenyldihexylphospholyl 1,2-didecynyldiphosphandiyl methyl(thienyl)indenyltrimethylthienyl 1,2-diundecynyldiphosphandiyl methyl(furanyl)indenyltrimethylfuranyl 1,2-didodecynyldiphosphandiyl methyl(pyrrolyl)indenyltrimethylpyrrolyl 1,2-dicyclopropyldiphosphandiylmethyl(phospholyl)indenyl trimethylphospholyl1,2-dicyclobutyldiphosphandiyl methyl(methylthienyl)indenylbenzothiopheneyl 1,2-dicyclopentyldiphosphandiylmethyl(methylfuranyl)indenyl benzofuranyl 1,2-dicyclohexyldiphosphandiylmethyl(methylpyrrolyl)indenyl phenylthienyl1,2-dicycloheptyldiphosphandiyl methyl(methylphospholyl)indenylphenylfuranyl 1,2-dicyclooctyldiphosphandiylmethyl(dimethylthienyl)indenyl phenylpyrrolyl1,2-dicyclononyldiphosphandiyl methyl(dimethylfuranyl)indenylphenylphospholyl 1,2-dicyclodecyldiphosphandiylmethyl(dimethylpyrrolyl)indenyl tolylthienyl 1,2-diphenyldiphosphandiylmethyl(dimethylphospholyl)indenyl tolylfuranyl 1,2-ditolyldiphosphandiylmethyl(ethylthienyl)indenyl tolylpyrrolyl 1,2-dimesityldiphosphandiylmethyl(ethylfuranyl)indenyl tolylphospholyl1,2-di(ethylphenyl)diphosphandiyl methyl(ethylpyrrolyl)indenylmesitylthienyl 1,2-di(propylphenyl)diphosphandiylmethyl(ethylphospholyl)indenyl mesitylfuranyl1,2-di(butylphenyl)diphosphandiyl methyl(propylthienyl)indenylmesitylpyrrolyl 1,2-di(pentylphenyl)diphosphandiylmethyl(propylfuranyl)indenyl mesitylphospholyl1,2-di(hexylphenyl)diphosphandiyl methyl(propylpyrrolyl)indenylfluorophenyl 1,2-di(dimethylphenyl)diphosphandiylmethyl(propylphospholyl)indenyl difluorophenyl1,2-di(trimethylphenyl)diphosphandiyl methyl(butylthienyl)indenyltrifluorophenyl 1,2-dibiphenyldiphosphandiyl methyl(butylfuranyl)indenyltetrafluorophenyl 1,2-diphenethyldiphosphandiylmethyl(butylpyrrolyl)indenyl pentafluorophenyl1,2-dinapthyldiphosphandiyl methyl(butylphospholyl)indenyltrifluoromethylphenyl 1,2-dinorbornyldiphosphandiylpropyl(benzothiopheneyl)indenyl fluorobenzyl1,2-diadamantyldiphosphandiyl propyl(benzofuranyl)indenyl difluorobenzyl1,2-di(fluoromethyl)diphosphandiyl propyl(fluorophenyl)indenyltrifluorobenzyl 1,2-di(fluoroethyl)diphosphandiylpropyl(difluorophenyl)indenyl tetrafluorobenzyl1,2-di(fluoropropyl)diphosphandiyl propyl(trifluorophenyl)indenylpentafluorobenzyl 1,2-di(fluorobutyl)diphosphandiylpropyl(tetrafluorophenyl)indenyl trifluoromethylbenzyl1,2-di(fluoropentyl)diphosphandiyl propyl(pentafluorophenyl)indenyl1,2-di(fluorohexyl)diphosphandiyl propyl(trifluoromethylphenyl)indenyl1,2-dithienyldiphosphandiyl propyl(thienyl)indenyl1,2-difuranyldiphosphandiyl propyl(furanyl)indenyl1,2-dipyrrolyldiphosphandiyl propyl(pyrrolyl)indenyl1,2-diphospholyldiphosphandiyl propyl(phospholyl)indenyl1,2-di(methylthienyl)diphosphandiyl propyl(methylthienyl)indenyl1,2-di(methylfuranyl)diphosphandiyl propyl(methylfuranyl)indenyl1,2-di(methylpyrrolyl)diphosphandiyl propyl(methylpyrrolyl)indenyl1,2-di(methylphospholyl)diphosphandiyl propyl(methylphospholyl)indenyl1,2-di(fluorophenyl)diphosphandiyl propyl(dimethylthienyl)indenyl1,2-di(difluorophenyl)diphosphandiyl propyl(dimethylfuranyl)indenyl1,2-di(trifluorophenyl)diphosphandiyl propyl(dimethylpyrrolyl)indenyl1,2-di(tetrafluorophenyl)diphosphandiylpropyl(dimethylphospholyl)indenyl1,2-di(pentafluorophenyl)diphosphandiyl propyl(ethylthienyl)indenyl1,2-dibenzyldiphosphandiyl propyl(ethylfuranyl)indenyl1,2-di(trifluoromethyl)diphosphandiyl propyl(ethylpyrrolyl)indenylpropyl(ethylphospholyl)indenyl 1-methyl-2-phenyldiphosphandiylpropyl(propylthienyl)indenyl 1-ethyl-2-phenyldiphosphandiylpropyl(propylfuranyl)indenyl 1-propyl-2-phenyldiphosphandiylpropyl(propylpyrrolyl)indenyl 1-butyl-2-phenyldiphosphandiylpropyl(propylphospholyl)indenyl 1-pentyl-2-phenyldiphosphandiylpropyl(butylthienyl)indenyl 1-hexyl-2-phenyldiphosphandiylpropyl(butylfuranyl)indenyl 1-heptyl-2-phenyldiphosphandiylpropyl(butylpyrrolyl)indenyl 1-octyl-2-phenyldiphosphandiylpropyl(butylphospholyl)indenyl 1-nonyl-2-phenyldiphosphandiyltetrahydroindenyl 1-decyl-2-phenyldiphosphandiyl methyltetrahydroindenyl1-methyl-2-tolyldiphosphandiyl dimethyltetrahydroindenyl1-ethyl-2-tolyldiphosphandiyl trimethyltetrahydroindenyl1-propyl-2-tolyldiphosphandiyl tetramethyltetrahydroindenyl1-butyl-2-tolyldiphosphandiyl pentamethyltetrahydroindenyl1-pentyl-2-tolyldiphosphandiyl hexamethyltetrahydroindenyl1-hexyl-2-tolyldiphosphandiyl ethyltetrahydroindenyl1-heptyl-2-tolyldiphosphandiyl propyltetrahydroindenyl1-octyl-2-tolyldiphosphandiyl butyltetrahydroindenyl1-nonyl-2-tolyldiphosphandiyl pentyltetrahydroindenyl1-decyl-2-tolyldiphosphandiyl hexyltetrahydroindenyl1-methyl-2-ethyldiphosphandiyl heptyltetrahydroindenyl1-methyl-2-propyldiphosphandiyl octyltetrahydroindenyl1-methyl-2-butyldiphosphandiyl nonyltetrahydroindenyl1-methyl-2-pentyldiphosphandiyl decyltetrahydroindenyl1-methyl-2-hexyldiphosphandiyl phenyltetrahydroindenyl1-methyl-2-heptyldiphosphandiyl methylphenyltetrahydroindenyl1-methyl-2-octyldiphosphandiyl ethylphenyltetrahydroindenyl1-methyl-2-nonyldiphosphandiyl propylphenyltetrahydroindenyl1-methyl-2-decyldiphosphandiyl butylphenyltetrahydroindenyl1-ethyl-2-propyldiphosphandiyl pentylphenyltetrahydroindenyl1-ethyl-2-butyldiphosphandiyl hexylphenyltetrahydroindenyl1-ethyl-2-pentyldiphosphandiyl heptylphenyltetrahydroindenyl1-ethyl-2-hexyldiphosphandiyl octylphenyltetrahydroindenyl1-ethyl-2-heptyldiphosphandiyl nonylphenyltetrahydroindenyl1-ethyl-2-octyldiphosphandiyl decylphenyltetrahydroindenyl1-ethyl-2-nonyldiphosphandiyl dimethylphenyltetrahydroindenyl1-ethyl-2-decyldiphosphandiyl trimethylphenyltetrahydroindenyl1-propyl-2-butyldiphosphandiyl dipropylphenyltetrahydroindenyl1-propyl-2-penyldiphosphandiyl methylpropylphenyltetrahydroindenyl1-propyl-2-hexyldiphosphandiyl tolyltetrahydroindenyl1-propyl-2-heptyldiphosphandiyl methyltolyltetrahydroindenyl1-propyl-2-octyldiphosphandiyl ethyltolyltetrahydroindenyl1-propyl-2-nonyldiphosphandiyl propyltolyltetrahydroindenyl1-propyl-2-decyldiphosphandiyl butyltolyltetrahydroindenyl1-butyl-2-pentyldiphosphandiyl dimethyltolyltetrahydroindenyl1-butyl-2-hexyldiphosphandiyl trimethyltolyltetrahydroindenyl1-butyl-2-heptyldiphosphandiyl dipropyltolyltetrahydroindenyl1-butyl-2-octyldiphosphandiyl methylpropyltolyltetrahydroindenyl1-butyl-2-nonyldiphosphandiyl naphthyltetrahydroindenyl1-butyl-2-dectkdiphosphandiyl methylnaphthyltetrahydroindenyl1-pentyl-2-hexyldiphosphandiyl ethylnaphthyltetrahydroindenyl1-pentyl-2-heptyldiphosphandiyl propylnaphthyltetrahydroindenyl1-pentyl-2-octyldiphosphandiyl butylnaphthyltetrahydroindenyl1-pentyl-2-nonyldiphosphandiyl dimethylnaphthyltetrahydroindenyl1-pentyl-2-decyldiphosphandiyl trimethylnaphthyltetrahydroindenyl1-hexyl-2-heptyldiphosphandiyl dipropylnaphthyltetrahydroindenyl1-hexyl-2-octyldiphosphandiyl methylpropylnaphthyltetrahydroindenyl1-hexyl-2-nonyldiphosphandiyl (propylphenyl)tetrahydroindenyl1-hexyl-2-decyldiphosphandiyl methyl(propylphenyl)tetrahydroindenyl1-heptyl-2-octyldiphosphandiyl ethyl(propylphenyl)tetrahydroindenyl1-heptyl-2-octyldiphosphandiyl propyl(propylphenyl)tetrahydroindenyl1-heptyl-2-nonyldiphosphandiyl butyl(propylphenyl)tetrahydroindenyl1-heptyl-2-decyldiphosphandiyl dimethyl(propylphenyl)tetrahydroindenyl1-octyl-2-nonyldiphosphandiyl trimethyl(propylphenyl)tetrahydroindenyl1-octyl-2-decyldiphosphandiylmethylpropyl(propylphenyl)tetrahydroindenyl1-nonyl-2-decyldiphosphandiyl (dipropylphenyl)tetrahydroindenylmethyl(dipropylphenyl)tetrahydroindenylethyl(dipropylphenyl)tetrahydroindenylpropyl(dipropylphenyl)tetrahydroindenylbutyl(dipropylphenyl)tetrahydroindenyldimethyl(dipropylphenyl)tetrahydroindenyltrimethyl(dipropylphenyl)tetrahydroindenylmethylpropyl(dipropylphenyl)tetrahydroindenyl(dimethylphenyl)tetrahydroindenylmethyl(dimethylphenyl)tetrahydroindenylethyl(dimethylphenyl)tetrahydroindenylpropyl(dimethylphenyl)tetrahydroindenylbutyl(dimethylphenyl)tetrahydroindenyltrimethyl(dimethylphenyl)tetrahydroindenyltrimethyl(dimethylphenyl)tetrahydroindenylmethylpropyl(dimethylphenyl)tetrahydroindenyl(trimethylphenyl)tetrahydroindenylmethyl(trimethylphenyl)tetrahydroindenylethyl(trimethylphenyl)tetrahydroindenylpropyl(trimethylphenyl)tetrahydroindenylbutyl(trimethylphenyl)tetrahydroindenyldimethyl(trimethylphenyl)tetrahydroindenyltrimethyl(trimethylphenyl)tetrahydroindenylmethylpropyl(trimethylphenyl)tetrahydroindenyl cyclopentadienylmethylcyclopentadienyl dimethylcyclopentadienyltrimethylcyclopentadienyl tetramethylcyclopentadienylethylcyclopentadienyl diethylcyclopentadienyl triethylcyclopentadienyltetraethylcyclopentadienyl propylcyclopentadienyldipropylcyclopentadienyl tripropylcyclopentadienyltetrapropylcyclopentadienyl butylcyclopentadienyldibutylcyclopentadienyl tributylcyclopentadienyltetrabutylcyclopentadienly pentylcyclopentadienyldipentylcyclopentadienyl tripentylcyclopentadienyltetrapentylcyclopentadienly hexylcyclopentadienyldihexylcyclopentadienyl trihexylcyclopentadienyltetrahexylcyclopentadienly heptylcyclopentadienyldiheptylcyclopentadienyl octylcyclopentadienyl dioctylcyclopentadienylnonylcyclopentadienyl dinonylcyclopentadienyl decylcyclopentadienyldidecylcyclopentadienyl undecylcyclopentadienyl dodecylcyclopentadienyltridecylcyclopentadienyl tetradecylcyclopentadienylpentadecylcyclopentadienyl hexadecylcyclopentadienylheptadecylcyclopentadienyl octadecylcyclopentadienylnonadecylcyclopentadienyl eicosylcyclopentadienylheneicosylcyclopentadienyl docosylcyclopentadienyltricosylcyclopentadienyl tetracosylcyclopentadienylpentacosylcyclopentadienyl hexacosylcyclopentadienylheptacosylcyclopentadienyl octacosylcyclopentadienylnonacosylcyclopentadienyl triacontylcyclopentadienylvinylcyclopentadienyl allylcyclopentadienyl propenylcyclopentadienylbutenylcyclopentadienyl propynylcyclopentadienyl butynylcyclopentadienylcyclopropylcyclopentadienyl cyclobutylcyclopentadienylcyclopentylcyclopentadienyl cyclohexylcyclopentadienylphenylcyclopentadienyl (dimethylphenyl)cyclopentadienyltolylcyclopentadienyl benzylcyclopentadienyl phenethylcyclopentadienyltrimethylsilylcyclopentadienyl trimethylgermylcyclopentadienyltriethylsilylcyclopentadienyl dimethylethylsilylcyclopentadienylbiphenylcyclopentadienyl pyrenylcyclopentadienyltrifluoromethylcyclopentadienyl trifluoromethylmethylcyclopentadienylnorborn ylcyclopentadienyl methylethylcyclopentadienylmethylpropylcyclopentadienyl methylbutylylcyclopentadienylmethylphenylcyclopentadienyl methylcyclohexylcylopentadienylmethyltolylcyclopentadienyl trimethylsilylmethylcylopentadienylmethylbenzylcylopentadienyl methylphenethylcylopentadienylmethylvinylcylopentadienyl methylallylcylopentadienyl(benzothiopheneyl)cyclopentadienyl (benzofuranyl)cyclopentadienyl(fluorophenyl)cyclopentadienyl (difluorophenyl)cyclopentadienyl(trifluorophenyl)cyclopentadienyl (tetrafluorophenyl)cyclopentadienyl(pentafluorophenyl)cyclopentadienyl(trifluoromethylphenyl)cyclopentadienyl (thienyl)cyclopentadienyl(furanyl)cyclopentadienyl (pyrrolyl)cyclopentadienyl(phospholyl)cyclopentadienyl (methylthienyl)cyclopentadienyl(methylfuranyl)cyclopentadienyl (methylpyrrolyl)cyclopentadienyl(methylphospholyl)cyclopentadienyl (dimethylthienyl)cyclopentadienyl(dimethylfuranyl)cyclopentadienyl (dimethylpyrrolyl)cyclopentadienyl(dimethylphospholyl)cyclopentadienylmethyl(benzothiopheneyl)cyclopentadienylmethyl(benzofuranyl)cyclopentadienylmethyl(fluorophenyl)cyclopentadienylmethyl(difluorophenyl)cyclopentadienylmethyl(trifluorophenyl)cyclopentadienylmethyl(tetrafluorophenyl)cyclopentadienylmethyl(pentafluorophenyl)cyclopentadienylmethyl(trifluoromethylphenyl)cyclopenta-dienylmethyl(thienyl)cyclopentadienyl methyl(furanyl)cyclopentadienylmethyl(pyrrolyl)cyclopentadienyl methyl(phospholyl)cyclopentadienylmethyl(methylthienyl)cyclopentadienylmethyl(methylfuranyl)cyclopentadienylmethyl(methylpyrrolyl)cyclopentadienylmethyl(methylphospholyl)cyclopentadienylmethyl(dimethylthienyl)cyclopentadienylmethyl(dimethylfuranyl)cyclopentadienylmethyl(dimethylpyrrolyl)cyclopentadienylmethyl(dimethylphospholyl)cyclopentadienyl fluorenyl methylfluorenyldimethylfluorenyl trimethylfluorenyl tetramethylfluorenyl ethylfluorenyldiethylfluorenyl triethylfluorenyl tetraethylfluorenyl propylfluorenyldipropylfluorenyl tripropylfluorenyl tetrapropylfluorenyl butylfluorenyldibutylfluorenyl tributylfluorenyl tetrabutylfluorenyl pentylfluorenyldipentylfluorenyl tripentylfluorenyl tetrapentylfluorenyl hexylfluorenyldihexylfluorenyl trihexylfluorenyl tetrahexylfluorenyl heptylfluorenyldiheptylfluorenyl octylfluorenyl dioctylfluorenyl nonylfluorenyldinonylfluorenyl decylfluorenyl didecylfluorenyl dodecylfluorenyldidodecylfluorenyl trifluoromethylfluorenylbis(trifluoromethyl)fluorenyl trimethylsilylfluorenylbis(trimethylsilyl)fluorenyl cyclohexylfluorenylbis(cyclohexyl)fluorenyl phenylfluorenyl diphenylfluorenyltolylfluorenyl bis(tolyl)fluorenyl octahydrofluorenylmethyloctahydrofluorenyl dimethyloctahydrofluorenyltrimethyloctahydrofluorenyl tetramethyloctahydrofluorenylethyloctahydrofluorenyl diethyloctahydrofluorenylpropyloctahydrofluorenyl dipropyloctahydrofluorenylbutyloctahydrofluorenyl dibutyloctahydrofluorenylpentyloctahydrofluorenyl dipentyloctahydrofluorenylhexyloctahydrofluorenyl dihexyloctahydrofluorenylheptyloctahydrofluorenyl diheptyloctahydrofluorenyloctyloctahydrofluorenyl dioctyloctahydrofluorenylmethyloctahydrodibenzyl[b,h]fluorenyldimethyloctahydrodibenzyl[b,h]fluorenyltrimethyloctahydrodibenzyl[b,h]fluorenyltetramethyloctahydrodibenzyl[b,h]fluorenylpentamethyloctahydrodibenzyl[b,h]fluorenylhexamethyloctahydrodibenzyl[b,h]fluorenylheptamethyloctahydrodibenzyl[b,h]fluorenyloctamethyloctahydrodibenzyl[b,h]fluorenyl (benzothiopheneyl)fluorenyl(benzofuranyl)fluorenyl (fluorophenyl)fluorenyl(difluorophenyl)fluorenyl (trifluorophenyl)fluorenyl(tetrafluorophenyl)fluorenyl (pentafluorophenyl)fluorenyl(trifluoromethylphenyl)fluorenyl (thienyl)fluorenyl (furanyl)fluorenyl(pyrrolyl)fluorenyl (phospholyl)fluorenyl (methylthienyl)fluorenyl(methylfuranyl)fluorenyl (methylpyrrolyl)fluorenyl(methylphospholyl)fluorenyl (dimethylthienyl)fluorenyl(dimethylfuranyl)fluorenyl (dimethylpyrrolyl)fluorenyl(dimethylphospholyl)fluorenyl bis(benzothiopheneyl)fluorenylbis(benzofuranyl)fluorenyl bis(fluorophenyl)fluorenylbis(difluorophenyl)fluorenyl bis(trifluorophenyl)fluorenylbis(tetrafluorophenyl)fluorenyl bis(pentafluorophenyl)fluorenylbis(trifluoromethylphenyl)fluorenyl bis(thienyl)fluorenylbis(furanyl)fluorenyl bis(pyrrolyl)fluorenyl bis(phospholyl)fluorenylbis(methylthienyl)fluorenyl bis(methylfuranyl)fluorenylbis(methylpyrrolyl)fluorenyl bis(methylphospholyl)fluorenylbis(dimethylthienyl)fluorenyl bis(dimethylfuranyl)fluorenylbis(dimethylpyrrolyl)fluorenyl bis(dimethylphospholyl)fluorenylazacyclopentadienyl phosphacyclopentadienyl stibacyclopentadienylarsacyclopentadienyl boracyclopentadienyl methylazacyclopentadienylmethylphosphacyclopentadienyl methylstibacyclopentadienylmethylarsacyclopentadienyl methylboracyclopentadienyl1,2-diazacyclopentadienyl 1,2-diphosphacyclopentadienyl1,2-distibacyclopentadienyl 1,2-diarsacyclopentadienyl1,2-diboracyclopentadienyl 1,2-azaphosphacyclopentadienyl1,2-azastibacyclopentadienyl 1,2-azarsacyclopentadienyl1,2-azaboracyclopentadienyl 1,2-arsaphosphacyclopentadienyl1,2-arsastibacyclopentadienyl 1,2-arsaboracyclopentadienyl1,2-boraphosphacyclopentadienyl 1,2-borastibacyclopentadienyl1,2-phosphastibacyclopentadienyl 1,3-diazacyclopentadienyl1,3-diphosphacyclopentadienyl 1,3-distibacyclopentadienyl1,3-diarsacyclopentadienyl 1,3-diboracyclopentadienyl1,3-azaphosphacyclopentadienyl 1,3-azastibacyclopentadienyl1,3-azarsacyclopentadienyl 1,3-azaboracyclopentadienyl1,3-arsaphosphacyclopentadienyl 1,3-arsastibacyclopentadienyl1,3-arsaboracyclopentadienyl 1,3-boraphosphacyclopentadienyl1,3-borastibacyclopentadienyl 1,3-phosphastibacyclopentadienylpentadienyl methylpentadienyl dimethylpentadienyl trimethylpentadienyltetramethylpentadienyl pentamethylpentadienyl hexamethylpentadienylallyl methylallyl dimethylallyl trimethylallyl tetramethylallylboratabenzene methylboratabenzene phenylboratabenzeneN,N-dimethylaminoboratabenzene N,N-diethylaminoboratabenzeneN,N-dipropylaminoboratabenzene

In a preferred embodiment of formula 2, A is the same as the indenylligand bonded to M.

Particularly preferred embodiments of formula 2 include compounds where:

-   1) each R¹, R², R³, R⁴, R⁵, and R⁶ is, independently, selected from    hydrogen or from the group consisting of C1 to C30 hydrocarbyls,    preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,    octyl, nonyl, decyl, undecyl, dodecyl, phenyl, C7 to C30 substituted    phenyls, and all isomers thereof; more preferably each R¹, R², R³,    R⁴, R⁵, and R⁶ is, independently, selected from hydrogen or from the    group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl,    s-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, phenyl, tolyl,    mesityl, and naphthyl; and/or-   2) Y is selected from the group of diradicals consisting of PR,    RP—PR, RN—PR; and/or-   3) each R is, independently, selected from the group consisting of    C1 to C30 hydrocarbyls, preferably methyl, ethyl, propyl, butyl,    pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,    phenyl, C7 to C30 substituted phenyls, and all isomers thereof; more    preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, s-butyl,    i-butyl, t-butyl, n-hexyl, cyclohexyl, phenyl, tolyl, mesityl, and    naphthyl; and/or-   4) X is, independently, selected from the group consisting of    chloride, bromide, fluoride, iodide, hydride, and C1 to C30    hydrocarbyls, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, phenyl, benzyl, and all isomers thereof, or two X together    are selected from C4-C10 dienes, preferably butadiene,    methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene,    hexadiene, methylhexadiene, dimethylhexadiene, or from C1-C10    alkylidenes, preferably methylidene, ethylidene, propylidene, or    from C3-C10 alkyldiyls, preferably propandiyl, butandiyl,    pentandiyl, and hexandiyl; and/or-   5) M is Ti, Zr, or Hf; and/or-   6) A is selected from the group consisting of substituted or    unsubstituted indenyl, substituted or unsubstituted fluorenyl and    substituted or unsubstituted cyclopentadienyl, more preferably,    indenyl, methylindenyl, dimethylindenyl, methylphenylindenyl,    methyltolylindenyl, methyl(dipropylphenyl)indenyl,    methyl(dimethylphenyl)indenyl methylnaphthylindenyl,    tetrahydroindenyl, fluorenyl, octahydrofluorenyl, dibutylfluorenyl,    cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl,    propylcyclopentadienyl, butylcyclopentadienyl,    methylpropylcyclopentadienyl, methylbutylcyclopentadienyl,    dimethylcyclopentadienyl, trimethylcyclopentadienyl, and    tetramethylcyclopentadienyl.

Particularly preferred embodiments of formulae 3 include compoundswhere:

-   1) each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is,    independently, selected from hydrogen or from the group consisting    of C1 to C30 hydrocarbyls, preferably methyl, ethyl, propyl, butyl,    pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,    phenyl, C7 to C30 substituted phenyls, and all isomers thereof; more    preferably each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and    R¹² is independently, selected from hydrogen or from the group    consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, s-butyl,    i-butyl, t-butyl, n-hexyl, cyclohexyl, phenyl, tolyl, mesityl, and    naphthyl; and/or-   2) Y is selected from the group of diradicals consisting of PR,    RP—PR, RN—PR; and/or-   3) each R is, independently, selected from the group consisting of    C1 to C30 hydrocarbyls, preferably methyl, ethyl, propyl, butyl,    pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,    phenyl, C7 to C30 substituted phenyls, and all isomers thereof; more    preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, s-butyl,    i-butyl, t-butyl, n-hexyl, cyclohexyl, phenyl, tolyl, mesityl, and    naphthyl; and/or-   4) X is, independently, selected from the group consisting of    chloride, bromide, fluoride, iodide, hydride, and C1 to C30    hydrocarbyls, preferably methyl, ethyl, propyl, butyl, pentyl,    hexyl, phenyl, benzyl, and all isomers thereof, or two X together    are selected from C4-C 10 dienes, preferably butadiene,    methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene,    hexadiene, methylhexadiene, dimethylhexadiene, or from C1-C10    alkylidenes, preferably methylidene, ethylidene, propylidene, or    from C3-C10 alkyldiyls, preferably propandiyl, butandiyl,    pentandiyl, and hexandiyl, and/or-   5) M is Ti, Zr, or Hf.

A set of exemplary catalyst precursors is set out below. These are byway of example only and are not intended to list every catalystprecursor that is within the scope of the invention. Particularlypreferred transition metal compounds include:

-   2,2′-phenylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,2′-methylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,2′-ethylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,2′-propylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,2′-butylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dichloride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconium    dichloride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconium    dichloride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconium dichloride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconium dichloride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium dichloride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium dichloride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconium    dichloride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    dichloride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    dichloride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dichloride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    dichloride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,    1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,    1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,    1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dichloride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium dichloride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium dichloride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium dichloride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium dichloride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium dichloride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium    dichloride,-   2,2′-phenylphosphindiyl-bis(indenyl)zirconium dimethyl,-   2,2′-methylphosphindiyl-bis(indenyl)zirconium dimethyl,-   2,2′-ethylphosphindiyl-bis(indenyl)zirconium dimethyl,-   2,2′-propylphosphindiyl-bis(indenyl)zirconium dimethyl,-   2,2′-butylphosphindiyl-bis(indenyl)zirconium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconium    dimethyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dimethyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dimethyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dimethyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dimethyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dimethyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium    dimethyl,-   2,2′-phenylphosphindiyl-bis(indenyl)zirconium dibenzyl,-   2,2′-methylphosphindiyl-bis(indenyl)zirconium dibenzyl,-   2,2′-ethylphosphindiyl-bis(indenyl)zirconium dibenzyl,-   2,2′-propylphosphindiyl-bis(indenyl)zirconium dibenzyl,-   2,2′-butylphosphindiyl-bis(indenyl)zirconium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconium    dibenzyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dibenzyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dibenzyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dibenzyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    dibenzyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(indenyl)zirconium difluoride,-   2,2′-methylphosphindiyl-bis(indenyl)zirconium difluoride,-   2,2′-ethylphosphindiyl-bis(indenyl)zirconium difluoride,-   2,2′-propylphosphindiyl-bis(indenyl)zirconium difluoride,-   2,2′-butylphosphindiyl-bis(indenyl)zirconium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium difluoride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconium    difluoride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconium    difluoride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconium difluoride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconium difluoride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium difluoride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium difluoride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconium    difluoride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    difluoride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    difluoride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconium difluoride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconium    difluoride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconium    difluoride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium difluoride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium difluoride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium difluoride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium difluoride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium difluoride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium    difluoride,-   2,1′-phenylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-methylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-ethylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-propylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-butylphosphindiyl-bis(indenyl)zirconium dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dichloride,-   2,2′-phenylphosphindiyl-bis(indenyl)hafnium dichloride,-   2,2′-methylphosphindiyl-bis(indenyl)hafnium dichloride,-   2,2′-ethylphosphindiyl-bis(indenyl)hafnium dichloride,-   2,2′-propylphosphindiyl-bis(indenyl)hafnium dichloride,-   2,2′-butylphosphindiyl-bis(indenyl)hafnium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dichloride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafnium    dichloride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafnium    dichloride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium dichloride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium dichloride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium dichloride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium dichloride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium    dichloride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dichloride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dichloride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dichloride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dichloride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafnium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafnium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dichloride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium dichloride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium dichloride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium dichloride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium dichloride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium dichloride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium    dichloride,-   2,2′-phenylphosphindiyl-bis(indenyl)hafnium dimethyl,-   2,2′-methylphosphindiyl-bis(indenyl)hafnium dimethyl,-   2,2′-ethylphosphindiyl-bis(indenyl)hafnium dimethyl,-   2,2′-propylphosphindiyl-bis(indenyl)hafnium dimethyl,-   2,2′-butylphosphindiyl-bis(indenyl)hafnium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafnium    dimethyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dimethyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dimethyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dimethyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dimethyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafnium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafnium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadieny)hafnium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dimethyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium    dimethyl,-   2,2′-phenylphosphindiyl-bis(indenyl)hafnium dibenzyl,-   2,2′-methylphosphindiyl-bis(indenyl)hafnium dibenzyl,-   2,2′-ethylphosphindiyl-bis(indenyl)hafnium dibenzyl,-   2,2′-propylphosphindiyl-bis(indenyl)hafnium dibenzyl,-   2,2′-butylphosphindiyl-bis(indenyl)hafnium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafnium    dibenzyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dibenzyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dibenzyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dibenzyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dibenzyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafnium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafnium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    dibenzyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(indenyl)hafnium difluoride,-   2,2′-methylphosphindiyl-bis(indenyl)hafnium difluoride,-   2,2′-ethylphosphindiyl-bis(indenyl)hafnium difluoride,-   2,2′-propylphosphindiyl-bis(indenyl)hafnium difluoride,-   2,2′-butylphosphindiyl-bis(indenyl)hafnium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium difluoride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafnium    difluoride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafnium    difluoride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium difluoride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium difluoride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium difluoride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium difluoride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium    difluoride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium difluoride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium difluoride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium difluoride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium difluoride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafnium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafnium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafnium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafnium    difluoride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium difluoride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium difluoride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium difluoride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium difluoride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium difluoride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium    difluoride,-   2,2′-phenylphosphindiyl-bis(indenyl)titanium dichloride,-   2,2′-methylphosphindiyl-bis(indenyl)titanium dichloride,-   2,2′-ethylphosphindiyl-bis(indenyl)titanium dichloride,-   2,2′-propylphosphindiyl-bis(indenyl)titanium dichloride,-   2,2′-butylphosphindiyl-bis(indenyl)titanium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dichloride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titanium    dichloride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titanium    dichloride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium dichloride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium dichloride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium dichloride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium dichloride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium    dichloride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium dichloride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium dichloride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium dichloride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium dichloride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium dichloride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titanium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titanium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dichloride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dichloride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium dichloride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium dichloride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium dichloride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium dichloride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium dichloride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium    dichloride,-   2,2′-phenylphosphindiyl-bis(indenyl)titanium dimethyl,-   2,2′-methylphosphindiyl-bis(indenyl)titanium dimethyl,-   2,2′-ethylphosphindiyl-bis(indenyl)titanium dimethyl,-   2,2′-propylphosphindiyl-bis(indenyl)titanium dimethyl,-   2,2′-butylphosphindiyl-bis(indenyl)titanium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titanium    dimethyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dimethyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dimethyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titanium dimethyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dimethyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titanium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titanium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium    dimethyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titanium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titanium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dimethyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dimethyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium    dimethyl,-   2,2′-phenylphosphindiyl-bis(indenyl)titanium dibenzyl,-   2,2′-methylphosphindiyl-bis(indenyl)titanium dibenzyl,-   2,2′-ethylphosphindiyl-bis(indenyl)titanium dibenzyl,-   2,2′-propylphosphindiyl-bis(indenyl)titanium dibenzyl,-   2,2′-butylphosphindiyl-bis(indenyl)titanium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titanium    dibenzyl,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dibenzyl,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dibenzyl,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titanium dibenzyl,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    dibenzyl,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titanium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titanium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titanium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titanium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titanium    dibenzyl,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    dibenzyl,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium    dibenzyl,-   2,2′-phenylphosphindiyl-bis(indenyl)titanium difluoride,-   2,2′-methylphosphindiyl-bis(indenyl)titanium difluoride,-   2,2′-ethylphosphindiyl-bis(indenyl)titanium difluoride,-   2,2′-propylphosphindiyl-bis(indenyl)titanium difluoride,-   2,2′-butylphosphindiyl-bis(indenyl)titanium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium difluoride,-   2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titanium    difluoride,-   2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titanium    difluoride,-   2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium difluoride,-   2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium difluoride,-   2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium difluoride,-   2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium difluoride,-   2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium    difluoride,-   2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium difluoride,-   2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium difluoride,-   2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium difluoride,-   2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium difluoride,-   2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium difluoride,-   2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titanium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titanium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titanium    difluoride,-   2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-rhethyl-4-butylcyclopentadienyl)titanium    difluoride,-   2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium difluoride,-   2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium difluoride,-   2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium difluoride,-   2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium difluoride,-   2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium difluoride,-   2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium    difluoride, and the like.    Mixed Catalysts

Mixed catalyst systems can also be used, for example, the inventioncatalyst can be used in conjunction with a “second catalyst” in the samereactor or in a series of reactors where the invention catalyst producesoligomers, macromers, or polymers with olefinic end-groups, and the“second catalyst” incorporates these oligomers, macromers, or polymersinto a polymer backbone as a copolymer with other monomers, such asethylene, propylene, butene, and other C2 to C20 olefins. Alternatively,the invention catalyst can be used in conjunction with a second catalystin the same reactor or in a series of reactors where the second catalystproduces oligomers, macromers, or polymers with olefinic end-groups, andthe invention catalyst incorporates these oligomers, macromers, orpolymers into a polymer backbone as a copolymer with other monomers,such as ethylene, propylene, butene, and other C2 to C20 olefins. The“second catalyst” can be of the same family as the invention catalyst,or can be from a completely different catalyst family. Likewise, theinvention catalyst can be used in conjunction with a “second catalyst”in the same reactor or in a series of reactors where the inventioncatalyst and the “second catalyst” produces mixtures or blends ofpolymers.

Invention polymerization catalyst systems can comprise additional olefinpolymerization catalysts, sometimes referred to as the “secondcatalyst”. These additional olefin polymerization catalysts are any ofthose well known in the art to catalyze the olefin to polyolefinreaction. Some invention catalysts systems include Group-4-6metallocenes as additional olefin polymerization catalysts. Metallocenesinclude (un)bridged compounds containing one (mono(cyclopentadienyl)metallocenes) or two (bis(cyclopentadienyl) metallocenes)(un)substituted cyclopentadienyl ligand(s). In bridged metallocenes, asingle, cyclopentadienyl ligand connects to a heteroatom ligand withboth coordinating to the metal center, or two cyclopentadienyl ligandsconnect together with both cyclopentadienyl ligands coordinating to themetal center. Typical catalysts and their precursors are well known inthe art. Suitable description appears in the patent literature, forexample U.S. Pat. Nos. 4,871,705, 4,937,299, 5,324,800, EP-A-0418044,EP-A-0591756, WO-A-92/00333 and WO-A-94/01471. Some embodiments selectthe metallocene compounds from mono- orbis-cyclopentadienyl-substituted, Group-4, -5, and -6 metals in whichcyclopentadienyls are (un)substituted with one or more groups or arebridged to each other or to a metal-coordinated heteroatom. Someembodiments select similar metallocene compounds except they are notnecessarily bridged to each other or to a metal-coordinated heteroatom.See U.S. Pat. Nos. 5,278,264 and 5,304,614.

Some invention catalysts systems include the following additional olefinpolymerization catalysts. Metallocene compounds suitable for linearpolyethylene or ethylene-containing copolymer production (wherecopolymer means comprising at least two different monomers) areessentially those disclosed in WO-A-92/00333, WO 97/44370 and U.S. Pat.Nos. 5,001,205, 5,057,475, 5,198,401, 5,304,614, 5,308,816 and5,324,800. Selection of metallocene compounds for isotactic orsyndiotactic polypropylene blend production, and their syntheses, arewell-known in the patent and academic literature, e.g. Journal ofOrganometallic Chemistry 369, 359-370 (1989). Typically, those catalystsare stereorigid, asymmetric, chiral, or bridged-chiral metallocenes.Invention activators are suited for activating these types of catalystprecursors.

Likewise, some invention catalysts systems include the followingadditional olefin polymerization catalysts: monocyclopentadienylmetallocenes with Group-15 or -16 heteroatoms connected, through abridging group, to a cyclopentadienyl-ligand ring carbon. Both thecyclopentadienyl Cp-ligand and the heteroatom connect to a transitionmetal. Some embodiments select a Group-4 transition metal. Additionally,unbridged monocyclopentadienyl, heteroatom-containing Group-4 componentsof WO 97/22639 will function with this invention. Moreover, transitionmetal systems with high-oxidation-state, Group-5-10 transition-metalcenters are known and can serve as the additional olefin polymerizationcatalysts with invention catalyst systems. Invention catalyst systemscan use non-cyclopentadienyl, Group-4-5 precursor compounds as theadditional olefin polymerization catalysts. Non-cyclopentadienyl,Group-4-5 precursor compounds are activable to stable, discrete cationiccomplexes include those containing bulky, chelating, diamide ligands,such as described in U.S. Pat. No. 5,318,935 and “Conformationally RigidDiamide Complexes: Synthesis and Structure of Tantalum (III) AlkyneDerivatives”, D. H. McConville, et al, Organometallics 1995, 14,3154-3156. U.S. Pat. No. 5,318,935 describes bridged and unbridged,bis-amido catalyst compounds of Group-4 metals capable of □-olefinspolymerization. Bridged bis(arylamido) Group-4 compounds for olefinpolymerization are described by D. H. McConville, et al., inOrganometallics 1995, 14, 5478-5480. Synthetic methods and compoundcharacterization are presented. Further work appearing in D. H.McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridgedbis(arylamido) Group-4 compounds that are polymerization catalysts for1-hexene. Additional invention-suitable transition-metal compoundsinclude those described in WO 96/40805. Cationic Group-3- or Lanthanideolefin polymerization complexes are disclosed in copending U.S.application Ser. No. 09/408050, filed 29 Sep. 1999, and its equivalentPCT/US99/22690. A monoanionic bidentate ligand and two monoanionicligands stabilize those catalyst precursors; they are activable withthis invention” ionic cocatalysts. Other suitable Group-4-5non-metallocene catalysts are bimetallocyclic catalyst compoundscomprising two independently selected Group-4-5 metal atoms directlylinked through two bridging groups to form cyclic compounds.

Invention catalyst systems can use transition metal catalyst precursorsthat have a 2+ oxidation state as the additional olefin polymerizationcatalyst. Typical Ni²⁺ and Pd²⁺ complexes are diimines, see “New Pd(II)-and Ni(II)- Based Catalysts for Polymerization of Ethylene andα-Olefins”, M. Brookhart, et al, J. Am. Chem. Soc., 1995, 117,6414-6415, WO 96/23010 and WO 97/02298. See additionally the relatedbis(imino) Group-8 and -9 organometallic compounds described by V. C.Gibson and others in “Novel olefin polymerization catalysts based oniron and cobalt”, Chem. Commun., 849-850, 1998.

For a review of other potential catalysts used in combination or serieswith the invention catalysts, see S. D. Ittel and L. K. Johnson, Chem.Rev. 2000, 1000, 1169 and V. C. Gibson and S. K. Spitzmesser, Chem. Rev.2003, 103, 283.

Activators and Catalyst Activation

The catalyst precursors, when activated by a commonly known activatorsuch as methyl alumoxane, form active catalysts for the polymerizationor oligomerization of olefins. Activators that may be used includealumoxanes such as methyl alumoxane, modified methyl alumoxane, ethylalumoxane, iso-butyl alumoxane and the like; Lewis acid activatorsinclude triphenyl boron, tris-perfluorophenyl boron,tris-perfluorophenyl aluminum and the like; Ionic activators includedimethylanilinium tetrakis perfluorophenyl borate, triphenyl carboniumtetrakis perfluorophenyl borate, dimethylanilinium tetrakisperfluorophenyl aluminate, and the like.

A co-activator is a compound capable of alkylating the transition metalcomplex, such that when used in combination with an activator, an activecatalyst is formed. Co-activators include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methyl alumoxane, andaluminum alkyls such trimethyl aluminum, tri-isobutyl aluminum, triethylaluminum, and tri-isopropyl aluminum. Co-activators are typically onlyused in combination with Lewis acid activators and ionic activators whenthe pre-catalyst is not a dihydrocarbyl or dihydride complex.

The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R^(x)—Al—O)_(n), which is a cyclic compound, orR^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. In thegeneral alumoxane formula, R^(x) is independently a C1-C₂₀ alkylradical, for example, methyl, ethyl, propyl, butyl, pentyl, isomersthereof, and the like, and “n” is an integer from 1-50. Most preferably,R^(x) is methyl and “n” is at least 4. Methyl alumoxane and modifiedmethyl alumoxanes are most preferred. For further descriptions see, EP 0279 586, EP 0 594 218, EP 0 561 476, W094/10180 and U.S. Pat. Nos.4,665,208, 4,874,734, 4,908,463, 4,924,018, 4,952,540, 4,968,827,5,041,584, 5,091,352, 5,103,031, 5,157,137, 5,204,419, 5,206,199,5,235,081, 5,248,801, 5,329,032, 5,391,793, and 5,416,229.

When an alumoxane or modified alumoxane is used, thecatalyst-precursor-to-activator molar ratio is from about 1:3000 to10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-catalyst-precursorratio is 1:1 molar ratio.

Ionic activators (at times used in combination with a co-activator) maybe used in the practice of this invention. Preferably, discrete ionicactivators such as [Me₂PhNH][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄],[Me₂PhNH][B((C₆H₃-3,5-(CF₃)₂))₄], [Ph₃C][B((C₆H₃-3,5-(CF₃)₂))₄],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used. Preferred co-activators, when used, are alumoxanes such asmethyl alumoxane, modified alumoxanes such as modified methyl alumoxane,and aluminum alkyls such as tri-isobutyl aluminum, and trimethylaluminum.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) borate, a trisperfluorophenylboron metalloid precursor or a trisperfluoronaphthyl boron metalloidprecursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid(U.S. Pat. No. 5,942,459) or combination thereof.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Ionic catalysts can be prepared by reacting a transition metal compoundwith an activator, such as B(C₆F₆)₃, which upon reaction with thehydrolyzable ligand (X′) of the transition metal compound forms ananion, such as ([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components which areionic compounds or compositions. However preparation of activatorsutilizing neutral compounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies which is formed when the two compounds are combined and saidanion will be sufficiently labile to be displaced by olefinic diolefinicand acetylenically unsaturated substrates or other neutral Lewis basessuch as ethers, nitrites and the like. Two classes of compatiblenon-coordinating anions have been disclosed in EPA 277,003 and EPA277,004 published 1988: 1) anionic coordination complexes comprising aplurality of lipophilic radicals covalently coordinated to and shieldinga central charge-bearing metal or metalloid core, and 2) anionscomprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L**-H)_(d) ⁺(A^(d−))wherein L** is an neutral Lewis base;

-   H is hydrogen;-   (L**-H)⁺ is a Bronsted acid-   A^(d−) is a non-coordinating anion having the charge d−-   d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from theprecatalyst after alkylation.

The activating cation (L**-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the alkylated transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L**-H)_(d) ⁺ may also be amoiety such as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums; most preferably triphenylcarbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in combination with a co-activator inthe preparation of the improved catalysts of this invention aretri-substituted ammonium salts such as: trimethylammoniumtetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniumtetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,tri(tert-butyl)ammonium tetraphenylborate, N,N-dimethylaniliniumtetraphenylborate, N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts such as: di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and other salts such astri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenylborate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L**-H)_(d)⁺(A^(d−)) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in U.S.Patent Publication 2002/0058765 A1, published on 16 May 2002, and forthe instant invention, require the addition of a co-activator to thecatalyst pre-cursor.

The term “non-coordinating anion” (NCA) means an anion that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. An NCA coordinates weakly enough that aneutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center.“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those that are compatible, stabilizethe transition metal complex cation in the sense of balancing its ioniccharge at +1, yet retain sufficient lability to permit displacement byan ethylenically or acetylenically unsaturated monomer duringpolymerization. These types of cocatalysts sometimes use scavengers suchas but not limited to tri-iso-butyl aluminum, tri-n-octyl aluminum,tri-n-hexyl aluminum, triethylaluminum or trimethylaluminum.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the alkylated transition metal compounds. Thealkylated invention compound is formed from the reaction of the catalystpre-cursor and the co-activator. For example, tris(pentafluorophenyl)boron or aluminum act to abstract a hydrocarbyl ligand to yield aninvention cationic transition metal complex and stabilizingnoncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732 forillustrations of analogous Group-4 metallocene compounds. Also, see themethods and compounds of EP-A-0 495 375. For formation of zwitterioniccomplexes using analogous Group 4 compounds, see U.S. Pat. Nos.5,624,878; 5,486,632; and 5,527,929.

Additional neutral Lewis-acids are known in the art and are suitable forabstracting formal anionic ligands. See in particular the review articleby E. Y.-X. Chen and T. J. Marks, “Cocatalysts for Metal-CatalyzedOlefin Polymerization: Activators, Activation Processes, andStructure-Activity Relationships”, Chem. Rev., 100, 1391-1434 (2000).

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation.

When an ionic or neutral stoichiometric activator is used, thecatalyst-precursor-to-activator molar ratio is from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2. The catalyst-precursor-to-co-activatormolar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1;1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylalumoxane, modified methylalumoxane, mixtures of methylalumoxanewith dimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum withdimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is as previously defined above, and each Z isindependently R^(x) or a different univalent anionic ligand such ashalogen (Cl, Br, I), alkoxide (OR^(x)) and the like. Most preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,tri-iso-butylaluminum, tri-n-octylaluminum. tri-n-hexylaluminum,trimethylaluminum and the like. Preferred boron alkyls includetriethylboron. Scavenging compounds may also be alumoxanes and modifiedalumoxanes including methylalumoxane and modified methylalumoxane.

Supported Catalysts

The solubility of invention catalyst precursors allows for the readypreparation of supported catalysts. To prepare uniform supportedcatalysts, the catalyst precursor preferably dissolves in the chosensolvent. The term “uniform supported catalyst” means that the catalystprecursor, the activator and or the activated catalyst approach uniformdistribution upon the support's accessible surface area, including theinterior pore surfaces of porous supports. Some embodiments of supportedcatalysts prefer uniform supported catalysts; other embodiments show nosuch preference.

Invention supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizing orpolymerizing olefin in a heterogenous process. The catalyst precursor,activator, co-activator if needed, suitable solvent, and support may beadded in any order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100-200% of the pore volume). The mixture is optionally heated from30-200° C. during this time. The catalyst precursor may be added to thismixture as a solid, if a suitable solvent is employed in the previousstep, or as a solution. Or alternatively, this mixture can be filtered,and the resulting solid mixed with a catalyst precursor solution.Similarly, the mixture may be vacuum dried and mixed with a catalystprecursor solution. The resulting catalyst mixture is then stirred for 1minute to 10 hours, and the catalyst is either filtered from thesolution and vacuum dried or evaporation alone removes the solvent.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100-200% of the pore volume). Afterstirring, the residual solvent is removed under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible. The catalyst precursor may also besupported absent the activator; in that case, the activator (andco-activator if needed) is added to a slurry process's liquid phase. Forexample, a solution of catalyst precursor may be mixed with a supportmaterial for a period of about 1 minute to 10 hours. The resultingprecatalyst mixture may be filtered from the solution and dried undervacuum, or evaporation alone removes the solvent. The total,catalyst-precursor-solution volume may be greater than the support'spore volume, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100-200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides, for example magnesium chloride and resinous support materialssuch as polystyrene polyolefin or polymeric compounds or any otherorganic support material and the like. Some embodiments select inorganicoxide materials as the support material including Group-2, -3, -4, -5,-13, or -14 metal or metalloid oxides. Some embodiments select thecatalyst support materials to include silica, alumina, silica-alumina,and their mixtures. Other inorganic oxides may serve either alone or incombination with the silica, alumina, or silica-alumina. These aremagnesia, titania, zirconia, and the like. Lewis acidic materials suchas montmorillonite and similar clays may also serve as a support. Inthis case, the support can optionally double as the activator component.But additional activator may also be used.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Invention catalyst carriers may have a surface area of from 10-700 m²/g,a pore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m²/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 μm. Otherembodiments select a surface area of 100-400 m²/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Inventioncarriers typically have a pore size of 10-1000 Angstroms, alternatively50-500 Angstroms, or 75-350 Angstroms.

Invention catalysts are generally deposited on the support at a loadinglevel of 10-100 micromoles of catalyst precursor per gram of solidsupport; alternately 20-80 micromoles of catalyst precursor per gram ofsolid support; or 40-60 micromoles of catalyst precursor per gram ofsupport. But greater or lesser values may be used provided that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

Invention catalysts can be supported for gas-phase, bulk, or slurrypolymerization, or otherwise as needed. Numerous support methods areknown for catalysts in the olefin polymerization art, particularlyalumoxane-activated catalysts; all are suitable for this invention'sbroadest practice. See, for example, U.S. Pat. Nos. 5,057,475 and5,227,440. An example of supported ionic catalysts appears in WO94/03056. U.S. Pat. No. 5,643,847 and WO 96/04319A describe aparticularly effective method. A bulk or slurry process using thisinvention's supported metal complexes activated with alumoxane can beused for ethylene-propylene rubber as described in U.S. Pat. Nos.5,001,205 and 5,229,478. Additionally, those processes suit thisinvention's catalyst systems. Both polymers and inorganic oxides mayserve as supports, as is known in the art. See U.S. Pat. Nos. 5,422,325,5,427,991, 5,498,582 and 5,466,649, and international publications WO93/11172 and WO 94/07928.

Monomers

In a preferred embodiment the catalyst compounds of this invention areused to polymerize or oligomerize any unsaturated monomer or monomers.Preferred monomers include C₂ to C₁₀₀ olefins, preferably C₂ to C₆₀olefins, preferably C₂ to C₄₀ olefins preferably C₂ to C₂₀ olefins,preferably C₂ to C₁₂ olefins. In some embodiments preferred monomersinclude linear, branched or cyclic alpha-olefins, preferably C₂ to C₁₀₀alpha-olefins, preferably C₂ to C₆₀ alpha-olefins, preferably C₂ to C₄₀alpha-olefins preferably C₂ to C₂₀ alpha-olefins, preferably C₂ to C₁₂alpha-olefins. Preferred olefin monomers may be one or more of ethylene,propylene, butene, pentene, hexene, heptene, octene, nonene, decene,dodecene, 4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1,and 5-ethylnonene-1.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,cyclopentadiene, cyclopentene, 4-methylcyclopentene, cyclohexene,4-methylcyclohexene, cyclobutene, vinyladamantane, norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-butylylnorbornene, 5-pentylnorbornene, 5-hexylnorbornene,5-heptylnorbornene, 5-octylnorbornene, 5-nonylnorbornene,5-decylnorbornene, 5-phenylnorbornene, vinylnorbornene, ethylidenenorbornene, 5,6-dimethylnorbornene, 5,6-dibutylnorbornene and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e. di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably and C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene. Dienes may beused in the processes described herein, preferably alpha-omega-dienesare used alone or in combination with mono-alpha olefins.

In a preferred embodiment the process described herein may be used toproduce homopolymers or copolymers. (For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units.) Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1, 3,5,5-trimethylhexene-1, cyclopentene,4-methylcyclopentene, cyclohexene, and 4-methylcyclohexene.

In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably the polymer produced hereinis a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1, 3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment the copolymers described herein comprise atleast 50 mole % of a first monomer and up to 50 mole % of othermonomers.

In another embodiment, the polymer comprises:

-   -   a first monomer present at from 40 to 95 mole %, preferably 50        to 90 mole %, preferably 60 to 80 mole %, and    -   a comonomer present at from 5 to 60 mole %, preferably 10 to 40        mole %, more preferably 20 to 40 mole %, and    -   a termonomer present at from 0 to 10 mole %, more preferably        from 0.5 to 5 mole %, more preferably 1 to 3 mole %.

In a preferred embodiment the first monomer comprises one or more of anyC₃ to C₈ linear branched or cyclic alpha-olefins, including propylene,butene, (and all isomers thereof), pentene (and all isomers thereof),hexene (and all isomers thereof), heptene (and all isomers thereof), andoctene (and all isomers thereof). Preferred monomers include propylene,1-butene, 1-hexene, 1-octene, cyclopentene, cyclohexene, cyclooctene,hexadiene, cyclohexadiene and the like.

In a preferred embodiment the comonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the termonomer comprises one or more of any C₂to C₄₀ linear, branched or cyclic alpha-olefins, (provided ethylene, ifpresent, is present at 5 mole % or less), including ethylene, propylene,butene, pentene, hexene, heptene, and octene, nonene, decene, undecene,dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene,octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the polymers described above further compriseone or more dienes at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Polymerization Processes

Invention catalyst complexes are useful in polymerizing unsaturatedmonomers conventionally known to undergo metallocene-catalyzedpolymerization such as solution, slurry, gas-phase, and high-pressurepolymerization. Typically one or more transition metal compounds, one ormore activators, and one or more monomers are contacted to producepolymer. These catalysts may be supported and as such will beparticularly useful in the known, fixed-bed, moving-bed, fluid-bed,slurry, solution, or bulk operating modes conducted in single, series,or parallel reactors.

One or more reactors in series or in parallel may be used in the presentinvention. The transition metal compound, activator and when required,co-activator, may be delivered as a solution or slurry, eitherseparately to the reactor, activated in-line just prior to the reactor,or preactivated and pumped as an activated solution or slurry to thereactor. Polymerizations are carried out in either single reactoroperation, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the precatalyst is activated in the reactor in the presenceof olefin.

Ethylene-alpha-olefin (including ethylene-cyclic olefin andethylene-alpha-olefin-diolefin) elastomers of high molecular weight andlow crystallinity can be prepared utilizing the catalysts of theinvention under traditional solution processes or by introducingethylene gas into a slurry utilizing the alpha-olefin or cyclic olefinor mixture thereof with other monomers, polymerizable and not, as apolymerization diluent in which the catalyst suspension is suspended.Typical ethylene pressures will be between 10 and 1000 psig (69-6895kPa) and the polymerization diluent temperature will typically bebetween −10 and 160° C. The process can be carried out in a stirred tankreactor or a tubular reactor, or more than one reactor operated inseries or in parallel. See the general disclosure of U.S. Pat. No.5,001,205 for general process conditions. All documents are incorporatedby reference for description of polymerization processes, ionicactivators and useful scavenging compounds.

The invention catalyst compositions can be used individually or can bemixed with other known polymerization catalysts to prepare polymerblends. Monomer and catalyst selection allows polymer blend preparationunder conditions analogous to those using individual catalysts. Polymershaving increased MWD for improved processing and other traditionalbenefits available from polymers made with mixed catalyst systems canthus be achieved.

Generally, when using invention catalysts, particularly when they areimmobilized on a support, the complete catalyst system will additionallycomprise one or more scavenging compounds. Here, the term scavengingcompound means a compound that removes polar impurities from thereaction environment. These impurities adversely affect catalystactivity and stability. Typically, purifying steps are usually usedbefore introducing reaction components to a reaction vessel. But suchsteps will rarely allow polymerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds. Typically, the scavengingcompound will be an organometallic compound such as the Group-13organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025 andWO-A-91/09882, WO-A-94/03506, WO-A-93/14132, and that of WO 95/07941.Exemplary compounds include triethyl aluminum, triethyl borane,tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane, andtri-n-octyl aluminum. Those scavenging compounds having bulky or C₆-C₂₀linear hydrocarbyl substituents connected to the metal or metalloidcenter usually minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chainlinear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. Whenalumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfp)₄]⁻ or B(Pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In terms of polymer density, the polymers capable of production inaccordance the invention, can range from about 0.85 to about 0.95,preferably from 0.87 to 0.93, more preferably 0.89 to 0.920. Polymermolecular weights can range from about 3000 Mn to about 2,000,000 Mn orgreater. Molecular weight distributions can range from about 1.1 toabout 50.0, with molecular weight distributions from 1.2 to about 5.0being more typical. Pigments, antioxidants and other additives, as isknown in the art, may be added to the polymer.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661 and 5,668,228 all of which are fullyincorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment when high density polyethylene is desired then the reactortemperature is typically between 70 and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also in somesystems the presence of comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

In another preferred embodiment the catalyst system in is liquid formand is introduced into the gas phase reactor into a resin particle leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization into a particle lean zone, please see US5,693,727, which is incorporated by reference herein.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psig to 735 psig, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process should be operatedabove the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at a pressure of 3620 kPa to 4309 kPa and at a temperature inthe range of about 60° C. to about 104° C. depending on the desiredpolymer melting characteristics. Reaction heat is removed through theloop wall since much of the reactor is in the form of a double-jacketedpipe. The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 to 10 weight percent, preferably from about 2to about 7 weight percent, more preferably from about 2.5 to about 6weight percent, most preferably from about 3 to about 6 weight percent.

Another process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-iso-butylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-iso-butyl aluminum and anexcess of alumoxane or modified alumoxane.

Homogeneous, Bulk or Solution Phase Polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent. Temperature control in the reactor is obtained bybalancing the heat of polymerization and with reactor cooling by reactorjackets or cooling coils to cool the contents of the reactor, autorefrigeration, pre-chilled feeds, vaporization of liquid medium(diluent, monomers or solvent) or combinations of all three. Adiabaticreactors with pre-chilled feeds may also be used. The reactortemperature depends on the catalyst used. In general, the reactortemperature preferably can vary between about 0° C. and about 160° C.,more preferably from about 10° C. to about 140° C., and most preferablyfrom about 40° C. to about 120° C. In series operation, the secondreactor temperature is preferably higher than the first reactortemperature. In parallel reactor operation, the temperatures of the tworeactors are independent. The pressure can vary from about 1 mm Hg to2500 bar (25,000 MPa), preferably from 0.1 bar to 1600 bar (1-16,000MPa), most preferably from 1.0 to 500 bar (10-5000MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, international application WO 96/33227 and WO97/22639.

Medium and High Pressure Polymerizations

In the high pressure process for the polymerization of ethylene alone orin combination with C₃ to C₁₀ alpha-olefins and optionally othercopolymerizable olefins, the temperature of the medium within which thepolymerization reaction occurs is at least 120° C. and preferably above140° C. and may range to 350° C., but below the decompositiontemperature of said polymer product, typically from 310° C. to 325° C.Preferably, the polymerization is completed at a temperature within therange of 130° C. to 230° C. The polymerization is completed at apressure above 200 bar (20 MPa), and generally at a pressure within therange of 500 bar (50 MPa) to 3500 bar (350 MPa). Preferably, thepolymerization is completed at a pressure within the range from 800 bar(80 MPa) to 2500 bar (250 MPa).

For medium pressure process, the temperature within which thepolymerization reaction occurs is at least 80° C. and ranges from 80° C.to 250° C., preferably from 100° C. to 220° C., and should for a givenpolymer in the reactor, be above the melting point of said polymer so asto maintain the fluidity of the polymer-rich phase. The pressure can bevaried between 100 and 1000 bar for ethylene homopolymers and from 30bar (3 MPa) to 1000 bar (100 MPa), especially 50 bar (5 MPa) to 500 bar(50 MPa) for processes producing ethylene copolymers containing C₃ toC₁₀ olefins and optionally other copolymerizable olefins.

More recently, polymerization conditions for high pressure and ortemperature polymerizations to prepare propylene homopolymers andcopolymers of propylene with C₃ to C₁₀ olefins and optionally othercopolymerizable olefins have been reported. See US patent applications60/431,185 filed Dec. 5, 2002; 60/431,077, filed Dec. 5, 2002; and60/412,541, filed Sep. 20, 2002.

After polymerization and deactivation of the catalyst, the polymerproduct can be recovered by processes well known in the art. Any excessreactants may be flashed off from the polymer and the polymer obtainedextruded into water and cut into pellets or other suitable comminutedshapes. For general process conditions, see the general disclosure ofU.S. Pat. Nos. 5,084,534, 5,408,017, 6,127,497, 6,255,410, which areincorporated herein by reference.

Experimental—Synthesis of Pre-catalysts

All manipulations with air and moisture sensitive compounds wereperformed either in an atmosphere of thoroughly purified argon using astandard Schlenk technique or in a controlled atmosphere Glove Box(Vacuum Atmospheres Co.). Tetrahydrofuran (THF, Merck=Merck KGaA,Darmstadt, Germany) and diethyl ether (ether, Merck) for synthesis werepurified by distillation over LiAlH₄, and stored over sodiumbenzophenone ketyl under an inert atmosphere; prior to use, the solventswere distilled from the benzophenone ketyl. Hydrocarbon solvents such asbenzene (Merck), toluene (Merck) and hexanes (Merck) were typicallydistilled over CaH₂, and were stored over Na/K alloy under an inertatmosphere; prior to use, the solvents were distilled from the Na/Kalloy. Methylene chloride-d₂ was distilled and stored over CaH₂ under aninert atmosphere; prior to use, the solvent was distilled from the CaH₂.Chloroform-d was distilled over P₄O₁₀ and stored over molecular sieves(3 Å). Iodobenzene (Acros=Acros Organics), indene, tech. (Acros),triethyl phosphite (Acros), LiAlH₄ (Aldrich=Aldrich Chemical Co.), PCl₅(Merck), HSiCl₃ (Aldrich), NaN(TMS)₂ (Aldrich, TMS=trimethylsilyl),NiCl₂ (Alfa Aesar), MeLi in ether (Aldrich), and ^(t)BuMgCl in ether(Aldrich) were used as obtained. Triethylamine (Acros) was dried withCaH₂, then was distilled from sodium. 2-Bromo-1H-indene [1,2], Pd(PPh₃)₄[4], ZrCl₄(THF)₂ [5], and ^(t)BuPH₂ [7] were prepared according to thepublished methods ([1]. McEwen, I.; Rönnqvist, M.; Ahlberg, P. J. Am.Chem. Soc. 1993, 115, 3989; [2]. Halterman, R. L.; Fahey, D. R.; Bailly,E. F.; Dockter, D. W.; Stenzel, O.; Shipman, J. L.; Khan, M. A.;Dechert, S.; Schumann, H. Organometallics 2000, 19, 5464; [4]. Coulson,D. R. Inorg. Synth. 1972, 13, 121; [5]. Manzer, L. E. Inorg. Synth.1982, 22, 135; [7]. Becker, G.; Rossler, O.; Schneider, E. Z. Anorg.Allg. Chem. 1978, 443, 42.

Analytical and semi-preparative liquid chromatography was performedusing Waters Delta 600 HPLC system including 996 Photodiode ArrayDetector, Nova-Pack C18 or HR Silica (60A, 6 μm, 3.9 and 19×300 mm) andSymmetry C18 (5 μm, 4.6×250 mm) columns. MPHPLC was performed usingMPHPLC glass columns and fittings (Ace Glass), PD5130 pump driveequipped with J1 gear-well pump head (Heidolph), 996 Photodiode ArrayDetector and Fraction Collector II (Waters Corp.).

¹H, ¹³C, and ³¹P spectra were recorded with a Brucker DPX-300 for 1-10%solutions in deuterated solvents. Chemical shifts for ¹H and ¹³C weremeasured relatively to tetramethylsilane (TMS). Chemical shifts for ³¹Pwere measured relatively to H₃PO₄. In ¹H NMR spectra, the assignment wasmade on the evidence of double resonance and Nuclear Overhauser Effect(NOE) experiments. C, H microanalyses were done using CHN-O-Rapidanalyzer (Heraecus Ltd., Banau, Germany).Trichloro(1H-iden-2-yl)phosphonium hexachlorophosphate (1-) (1).

To a suspension of 154 g (0.74 mol) of PCl₅ in 200 ml of toluene, asolution of 48.2 ml (43.0 g, 0.37 mol) of indene (tech., 90%) in 30 mlof toluene was added by vigorous stirring (mechanical stirrer) for 30min at 0° C. The resulted mixture was stirred for 10 hours at ambienttemperature. Then, the precipitate was filtered off (G3), washed with3×50 ml of hexanes, and dried in vacuum. Yield 165 g (90%) of whitesolid, which was further used without an additional purification.1H-Inden-2-ylphosphonous dichloride (2).

To a suspension of 4.96 g (10 mmol) of 1 in 50 ml of toluene, 2.22 ml(2.98 g, 22 mmol) of HSiCl₃ was added at ambient temperature. Thismixture was refluxed for 6 hours to form clear yellow solution. Volatilecomponents were distilled off at 50° C., and the yellow oil formed wasdried in vacuum at this temperature. The crystalline material formed ispure 1H-Inden-2-ylphosphonous dichloride, 2. Yield 2.17 g (99%).

Anal. calc. for C₉H₇Cl₂P: C, 49.81; H, 3.25. Found: C, 49.67; H, 3.18.

¹H NMR (C₆D₆): δ 7.14-7.17 (m, 4H, 4,5,6,7-H), 6.92 (dt, J=8.1 Hz, J=1.7Hz, 1H, 3-H), 3.61 (d, J=1.7 Hz, 2H, 1,1′-H).

¹³C{¹H} NMR (C₆D₆): δ 147.2 (d, J=54.9 Hz), 145.9 (d, J=2.8 Hz), 144.1(d, J=54.9 Hz), 142.2 (d, J=12.2 Hz), 127.8, 127.0, 124.3, 123.2, 37.9.

³¹P{¹H} NMR (C₆D₆): δ 151.4.Diethyl 1H-inden-2-ylphosphonate (9).

To 91.0 g (0.467 mol) of 2-bromo-1H-indene and 3.02 g (0.023 mol) ofNiCl₂ in 250 ml flask equipped with a distillation head, 85.0 ml (82.4g, 0.496 mol) of (EtO)₃P were added. This black mixture was heated inthe oil bath at 185-190° C. for 3 hours. During this procedure, argongas was bubbled through the mixture to eliminate ethyl bromide formed.The crude product was distilled in vacuum (171-175° C./1 mm). Yield102.4 g (87%) of colorless oil of diethyl 1H-inden-2-ylphosphonate, 9.

Anal. calc. for C₁₃H₁₇O₃P: C, 61.90; H, 6.79. Found: C, 62.03; H, 6.82.

¹H NMR (CDCl₃): δ 7.63 (m, 1H, 3-H), 7.51 (m, 2H, 4,7-H), 7.32 (m, 2H,5,6-H), 4.07-4.23 (m, 4H, OCH₂Me), 3.65 (m, 2H 1,1′-H in indenyl), 1.35(t, J=7.0 Hz, 6H, Me). ³¹P{¹H} NMR (CDCl₃): δ 31.2.tert-Butyl(1H-inden-2-yl)phonosphinous chloride (8).

To a solution of 1.09 g (5.0 mmol) of 2 in 40 ml of diethylether-hexanes (1: 1, vol.), 4.7 ml of 1.06 M ^(t)BuMgCl in ether wasadded dropwise at vigorous stirring for 2 hours at −90° C. The resultedmixture was slowly warmed to ambient temperature, stirred overnight, andfiltered through glass frit (G3). The precipitate was additionallywashed with 3×15 ml of ether. The combined filtrate was evaporated todryness, and the residue was dried in vacuum. Yield 1.19 g (99%) ofcolorless solid.

Anal. calc. for C₁₃H₁₆ClP: C, 65.41; H, 6.76. Found: C, 65.62; H, 7.85.

¹H NMR (C₆D₆): δ 7.15-7.34 (m, 5H, 3,4,5,6,7-H), 3.43-3.68 (m, 1,1′-H inindenyl), 1.11 (d, J=14.0 Hz, 9H, ^(t)Bu).

¹³C{1H} NMR (C₆D₆): δ 146.1, 144.5 (d, J=45.8 Hz), 144.1 (d, J=10.7 Hz),142.9 (d, J=35.1 Hz), 126.9, 126.2, 124.0, 121.9, 42.6 (d, J=6.1 Hz),34.8 (d, J=29.0 Hz), 25.8 (d, J=18.3 Hz).

³¹P{¹H} NMR (C₆D₆): δ 104.5.1H-Inden-2-ylphosphine (10), 1H-Indan-2-ylphosphine (11) and compound12.

To a suspension of 13.3 g (0.350 mol) of LiAlH₄ in 200 ml of ether, asolution of 58.7 g (0.233 mol) of 9 in 140 ml of ether was dropwise for2 hours. The resulting mixture was refluxed for 2 hours, then, cooled toroom temperature, and 50 ml of water was added dropwise to decompose anexcess of metal hydrides. The ether solution was separated, and theresidue was diluted with 2×200 ml of ether. The combined extract wasevaporated to ca. 100 ml. A white solid precipitated at −30° C. wasseparated, washed with 10 ml of cold ether and dried in vacuum. Yield:2.39 g (7%) of compound 12. The yellow solution was evaporated, and theobtained oil was distilled in vacuum (108-110° C./8 mm). Yield: 21.90 gof ca. 4 to 1 mixture of 10 (51%) and 11 (12%). Additional carefulfractional distillation of this mixture gave 14.52 g of 10 of 93% purity(³¹P NMR).

Compound 10.

Anal. calc. for C₉H₉P: C, 72.97; H, 6.12. Found: C, 72.85; H, 6.20.

¹H NMR (C₆D₆): δ 7.15-7.27 (m, 3H, 5,6,7-H), 7.06-7.12 (m, 1H, 3-H),6.83-6.87 (m, 1H, 4-H), 3.56 (m, J_(P-H)=199.6 Hz, 2H, PH₂), 3.05 (m,2H, 1,1′-H).

¹³C NMR (C₆D₆): δ 146.2, 145.3 (d, J=9.2 Hz), 142.0 (d, J=26.0 Hz),134.8 (d, J=13.7 Hz), 126.6, 125.2, 123.5, 120.8, 46.7. ³¹P NMR (C₆D₆):δ −131.6 (dt, J_(P-H)=199.6 Hz, J_(P-H)=7.8 Hz).

Compound 11.

³¹P NMR (C₆D₆): δ −102.6 (m, J_(P-H)=189.5 Hz, J_(P-H)=11.7 Hz,J_(P-H)=9.8 Hz).

Compound 12.

Anal. calc. for C₂₇H₂₃P₃: C, 73.64; H, 5.26. Found: C, 73.56; H, 5.20.

¹H NMR spectrum (in CD₂Cl₂), see FIG. 1.

³¹P{¹H} NMR (CD₂Cl₂): δ 36.2 (d, J_(P-P)=270.9 Hz), −26.0 (dd,J_(P-P)=235.9 Hz, J_(P-P)=270.9 Hz), −40.3 (d, J_(P-P)=235.9 Hz).

³¹P NMR (CD₂Cl₂): δ 36.2 (d, J_(P-P)=270.9 Hz), −26.0 (ddd,J_(P-P)=270.9 Hz, J_(P-P)=235.9 Hz, J_(P-H)=16.9 Hz), −40.3 (dddt,J_(P-P)=235.9 Hz, J_(P-H)=208.9 Hz, J_(P-H)=19.0 Hz, J_(P-H)=12.4 Hz).tert-Butyl(1H-inden-2-yl)phosphine (14).

To 9.61 g (0.049 mol) of 2-bromo-1H-indene and 1.13 g (0.98 mmol) ofPd(PPh₃)₄ in 25 ml of toluene, 7.5 ml (5.45 g, 0.054 mol) of Et₃N and4.88 g (0.054 mol) of ^(t)BuPH₂ were added. This mixture was refluxedfor 14 hours, cooled to room temperature, and filtered through glassfrit (G3) to separate out compound 15. The filtrate was evaporated todryness. The crude product was distilled in vacuum (108-110° C./3 mm).Yield 3.07 g (31%) of crystalline solid of 14.

Anal. calc. for C₁₃H₁₇P: C, 76.45; H, 8.39. Found: C, 76.32; H, 8.33.

¹H NMR (CDCl₃): δ 7.42 (m, 1H, 7-H), 7.36 (m, 1H, 4-H), 7.25 (m, 1H,5-H), 7.16 (m, 1H, 6-H), 7.06 (m, 1H, 3-H), 3.86 (br.s, 1H, PH), 3.56(m, 2H, 1,1′-H in indenyl), 1.18 (d, 9H, J=12.9 Hz, ^(t)Bu).

¹³C{¹H} NMR (CDCl₃): δ 145.9 (d, J=3.3 Hz), 145.1 (d, J=6.1 Hz), 141.4(d, J=19.8 Hz), 140.7 (d, J=16.8 Hz), 126.4, 124.8, 123.3, 120.6, 45.8(d, J=7.6 Hz), 30.2 (d, J=13.7 Hz), 29.4 (d, J=7.6 Hz).

³¹P{¹H} NMR (CDCl₃): δ −28.7 (d, J=207.4 Hz).tert-Butyl[di(1H-inden-2yl)]phosphine (15).

To 15.61 g (0.080 mol) of 2-bromo-1H-indene and 1.38 g (1.19 mmol) ofPd(PPh₃)₄ in 60 ml of toluene, 22.3 ml (16.19 g, 0.160 mol) of Et₃N and3.60 g (0.040 mol) of ^(t)BuPH₂ were added. This mixture was refluxedfor 24 hours, cooled to room temperature, and passed through shortcolumn with Silica Gel using 200 ml of toluene as eluent. The filtratewas evaporated to dryness to give oil, which after treatment with 150 mlof hot ethanol gave a gray precipitate. This precipitate was separated(G3), washed with 3×5 ml of cold ethanol and dried in vacuum. Yield10.83 g (85%) of 15.

Anal. calc. for C₂₂H₂₃P: C, 82.99; H, 7.28. Found: C, 82.71; H, 7.38.

¹H NMR (C₆D₆): δ 7.26 (m, 2H, 7-H), 7.23 (m, 2H, 5-H), 7.13-7.19 (m, 4H,3,6-H), 7.11 (m, 2H, 4-H), 3.42 (s, 4H, 1,1′-H in indenyl), 1.14 (d,J=12.6 Hz, 9H, ^(t)Bu).

¹³C{¹H} NMR (C₆D₆): δ 148.0 (d, J=4.6 Hz), 144.9 (d, J=9.2 Hz), 144.6(d, J=22.9 Hz), 141.8 (d, J=24.4 Hz), 126.8, 125.3,

8, 121.2, 43.9 (d, J=9.2 Hz), 31.0 (d, J=12.2 Hz), 29.0 (d, J=13.7 Hz).

³¹P{¹H} NMR (C₆D₆): δ −6.4.1H-Inden-2-yl(phenyl)phosphine (17).

To 7.40 g (0.050 mol) of 10 and 2.88 g (2.49 mmol) of Pd(PPh₃)₄ in 20 mlof toluene, 7.7 ml (5.59 g, 0.055 mol) of Et₃N and, then, 5.6 ml (10.21g, 0.050 mol) of iodobenzene were added. This mixture was refluxed for 8hours, cooled to room temperature, and passed through short column withSilica Gel using 30 ml of toluene as eluent. The resulted solution wasevaporated to dryness. The crude product was distilled in vacuum(120-121° C./2 mm). Yield 5.71 g (51%) of colorless oil of 17.

Anal. calc. for C₁₅H₁₃P: C, 80.34; H, 5.84. Found: C, 80.22; H, 5.90.

¹H NMR (C₆D₆): δ 7.08-7.68 (m, 10H, 3,4,5,6,7-H in indenyl and C₆H₅),5.13 (d, J=216.3 Hz, 1H, PH), 3.24 (m, 2H, 1,1′-H in indenyl).

¹³C{¹H} NMR (C₆D₆): δ 146.4 (d, J=3.1 Hz), 145.2 (d, J=9.2 Hz), 141.7(d, J=15.3 Hz), 141.4 (d, J=24.4 Hz), 134.0 (d, J=16.8 Hz), 128.8 (d,J=6.1 Hz), 128.6 (d, J=6.1 Hz), 128.5, 126.7, 125.4, 123.8, 121.2, 43.7(d, J=4.6 Hz).

³¹P{¹H} NMR (C₆D₆): δ −43.1 (d, J=211.3 Hz).Di(1H-inden-2yl)(phenyl)phosphine (16).

To 4.00 g (0.021 mol) of 2-bromo-1-indene and 0.46 g (0.40 mmol) ofPd(PPh₃)₄ in 20 ml of toluene, 3.2 ml (2.32 g, 0.023 mol) of Et₃N and,then, 4.52 g (0.020 mol) of 17 were added. This mixture was refluxed for13 hours, cooled to room temperature, and passed through short columnwith Silica Gel using 150 ml of toluene as eluent. The resulted solutionwas evaporated to dryness. The crude product was crystallized fromethanol. Yield 1.63 g (28%) of white crystals of 16.

Anal. calc. for C₂₄H₁₉P: C, 85.19; H, 5.66. Found: C, 85.01; H, 5.58.

¹H NMR (CDCl₃): δ 7.53 (m, 4H, 2,6-H in C₆H₅), 7.38 (m, 2H, 7-H inindenyl), 7.35 (m, 6H, 3,4,5-H in C₆H₅), 7.33 (m, 2H, 4-H in indenyl),7.16 (m, 2H, 5-H in indenyl), 7.24 (m, 2H, 6-H in indenyl), 7.01 (m, 2H,3-H in indenyl), 3.47 (m, 4H, 1,1′-H in indenyl).

¹³C{¹H} NMR (CDCl₃): δ 145.9 (d, J=3.1 Hz), 144.6 (d, J=7.6 Hz), 140.3(d, J=18.3 Hz), 136.5 (d, J=4.6 Hz), 133.7, (d, J=19.8 Hz), 129.1, 128.9(d, J=6.1 Hz), 126.6 (d, J=6.1 Hz), 126.5, 125.1, 123.6, 121.0, 42.1 (d,J=13.7 Hz).

³¹P{¹H} NMR (C₆D₆): δ −29.7.Mixture of d-/l- andmeso-1,2-di-tert-butyl-1,2-di(1H-inden-2yl)diphosphanes (18).

To a solution of 335 mg (1.74 mmol) of 14 in 3 ml of diethyl ether, 0.49ml (356 mg, 3.52 mmol) of triethylamine and 415 mg (1.74 mmol) of 8 wereadded at −78° C. The reaction mixture was slowly warmed to ambienttemperature at vigorous stirring. This mixture was additionally stirredfor 5 hours at room temperature, 100 hours at 40° C., and thenevaporated to dryness. The residue was dissolved in 50 ml of toluene. Inthe Glove Box, this solution was passed through a short column withSilica Gel 60 (d 20 mm,l 70 mm). This column was additionally washedwith 250 ml of toluene. The combined extract was evaporated to drynessto give a white solid. Yield 357 mg (51%) as a mixture of d-/l-(trans-)and meso-(cis-)isomers in ratio ca. 3 to 2.

Anal. calc. for C₂₆H₃₂P₂: C, 76.83; H, 7.93. Found: C, 76.99; H, 8.01.

d-/l-18.

¹H NMR (C₆D₆): δ 7.27 (m, 2H, 3-H in indenyl), 7.19 (m, 2H, 7-H inindenyl), 7.09 (m, 2H, 5-H in indenyl), 6.89 (m, 2H, 6-H in indenyl),6.76 (m, 2H, 4-H in indenyl), 3.12 (d, J=22.6 Hz, 2H, 1-H in indenyl),2.65 (d, J=22.6 Hz, 2H, 1′-H in indenyl), 1.27 (t, J=6.9 Hz, 18H,^(t)Bu).

¹³C NMR (C₆D₆): δ 148.8, 146.6, 144.7 (t, J=18.7 Hz), 144.3, 126.5,125.4, 123.6, 121.2, 43.4, 29.8 (t, J=11.5 Hz), 25.7.

³¹P{¹H} NMR (C₆D₆): δ −13.1 (max).

meso-18.

¹H NMR (C₆D₆): δ 7.48 (m, 2H, 3-H in indenyl), 7.24 (m, 2H, 7-H inindenyl), 7.07 (m, 2H, 5-H in indenyl), 7.04 (m, 2H, 6-H in indenyl),7.01 (m, 2H, 4-H in indenyl), 3.80 (d, J=22.9 Hz, 2H, 1-H in indenyl),3.55 (d, J=22.9 Hz, 2H, 1′-H in indenyl), 0.97 (t, J=6.4 Hz, 18H,^(t)Bu).

¹³C{¹H} NMR (C₆D₆): δ 148.5, 146.7, 145.5 (t, J=18.4 Hz), 144.0, 126.8,125.8, 124.0, 121.5, 44.3, 30.1 (t, J=9.3 Hz), 26.0.

³¹P{¹H} NMR (C₆D₆): δ −19.5 (min).

2,2′-tert-butylphosphindiyl-bis(η⁵-indenyl)zirconium dichloride—Complex25

To a solution of 4.66 g (14.6 mmol) of 15 in 130 ml of ether, 16.0 ml(29.2 mmol) of 1.83 M MeLi in ether were added at −90° C. This mixturewas stirred for 3 hours at ambient temperature, then, 5.37 g (14.2 mmol)of ZrCl₄(THF)₂ were added at −90° C. It was stirred for 48 hours at roomtemperature, and, then, filtered through glass frit (G4). Theprecipitate was washed with 5×100 ml of hot toluene. The combinedextract was evaporated to ⅔ of volume. Crystallization of the solutionat −30° C. gave yellow crystals of 25. Yield 3.81 g (56%).

Anal. calc. for C₂₂H₂₁Cl₂PZr: C, 55.22; H, 4.42. Found: C, 55.47; H,4.49.

¹H NMR (CD₂Cl₂): δ 7.57 (dq, J=8.5 Hz, J=1.0 Hz, 2H, 4/7-H in indenyl),7.42 (dq, J=8.5 Hz, J=1.0 Hz, 2H, 7/4-H in indenyl), 7.24 (ddd, J=8.5Hz, J=6.5 Hz, J=1.2 Hz, 2H, 5/6-H in indenyl), 7.17 (ddd, J=8.5 Hz,J=6.5 Hz, J=1.2 Hz, 2H, 5/6-H in indenyl), 6.62 (dt, J=2.6Hz, J=1.0 Hz,2H, 1/3-H in indenyl), 6.36 (ddd, J=5.6 Hz, J=2.6 Hz, J=1.0 Hz, 2H,3/1-H in indenyl), 1.58 (d, J=14.7 Hz, 9H, ^(t)Bu).

¹³C{¹H} NMR (CD₂Cl₂): δ 130.5 (d, J=7.9 Hz), 129.7 (d, J=17.2 Hz),128.7, 127.7, 126.4, 126.1, 114.7 (d, J=42.7 Hz), 110.9 (d, J=33.6 Hz),103.5 (d, J=7.6 Hz), 33.2 (d, J=15.3 Hz), 30.7 (d, J=16.8 Hz).

³¹P{¹H} NMR (CD₂Cl₂): δ −12.0.

A representation of the molecular structure of complex 25 is shown inFIG. 2.

2,2′-phenylphosphindiyl-bis(η⁵-indenyl)zirconium dichloride—Complex 26

To a solution of 1.48 g (4.37 mmol) of 16 in 50 ml of ether, 4.8 ml(8.75 mmol) of 1.84 M MeLi in ether was added at −90° C. This mixturewas stirred for 12 hours at ambient temperature, then, 1.65 g (4.37mmol) of ZrCl₄(THF)₂ was added at −90° C. It was stirred for 24 hours atroom temperature, then, evaporated to dryness. To the residue, 50 ml oftoluene was added, and this mixture was stirred additionally for 12hours. The orange slurry formed was filtered through glass frit (G4).The precipitate was washed with 50 ml of hot toluene. To the combinedtoluene extract, 60 ml of hexanes was added. Crystallization of thissolution at −30° C. gave orange crystals of 26. Yield 0.79 g (36%).

Anal. calc. for C₂₄H₁₇Cl₂PZr: C, 57.83; H, 3.44. Found: C, 58.11; H,3.56.

¹H NMR (C₆D₆): δ 7.53 (dq, J=8.5 Hz, J=1.0 Hz, 2H, 4/7-H in indenyl),7.41-7.47 (m, 2H, 2,6-H in C₆H₅), 7.26 (dq, J=8.5 Hz, J=1.0 Hz, 2H,7/4-H in indenyl), 6.98-7.20 (m, 3H, 3,4,5-H in C₆H₅), 6.96 (ddd, J=8.5Hz, J=6.7 Hz, J=1.2 Hz, 2H, 5/6-H in indenyl), 6.87 (ddd, J=8.5 Hz,J=6.7 Hz, J=1.2 Hz, 2H, 5/6-H in indenyl), 6.21 (ddd, J=4.4 Hz, J=2.6Hz, J=0.9 Hz, 2H, 1/3-H in indenyl), 5.97 (m, 2H, 3/1-H in indenyl).

¹³C{¹H} NMR (C₆D₆): δ 134.5, 134.1, 134.0, 131.2 (d, J=13.7 Hz), 129.2(d, J=4.1 Hz), 127.3, 126.8, 126.5, 125.1, 125.0, 109.7 (d, J=38.2 Hz),107.2 (d, J=27.5 Hz), 101.4 (d, J=7.6 Hz).

³¹P{¹H} NMR (C₆D₆): δ −30.4.2,2'-(1,2di-tert-butyldiphosphandiyl)-bis(η⁵-indenyl)zirconiumdichloride - Complex 27.

To a solution of 713 mg (1.75 mmol) of 18 in 15 ml of toluene, asolution of 642 mg (3.50 mmol) of NaN(TMS)₂ in 10 ml of toluene wasadded at ambient temperature. This mixture was stirred for 24 hours. Thewhite precipitate formed was filtered off (G3), washed with 3×30 ml ofhexanes, and dried in vacuum. To a suspension of this sodium salt in 25ml of diethyl ether, 660 mg (1.75 mmol) of ZrCl₄(THF)₂ was added. Theresulted mixture was stirred for 48 hours at ambient temperature andthen evaporated to dryness. The crude product was extracted with 30 mlof toluene. The toluene solution was filtered through glass frit (G4),and the filtrate was evaporated to ca. 10 ml. Crystals that precipitatedat −30° C. were collected, washed with 3×30 ml of hexanes, and dried invacuum. Yield 520 mg (52%) of pure rac-complex (trans-^(t)BuPPBu^(t)).

Anal. calc. for C₂₆H₃₀Cl₂P₂Zr: C, 55.12; H, 5.34. Found: C, 55.28; H,5.38.

¹H NMR (CD₂Cl₂): δ 7.52 (m, 2H, 4/7-H in indenyl), 7.42 (m, 2H, 7/4-H inindenyl), 7.20 (m, 2H, 5/6-H in indenyl), 7.12 (m, 2H, 5/6-H inindenyl), 6.85 (m, 2H, 1/3-H in indenyl), 6.62 (m, 2H, 3/1-H inindenyl), 1.19 (t, J=6.9 Hz, 18H, ^(t)Bu).

¹³C{¹H} NMR (CD₂Cl₂): δ 134.8, 130.9 (t, J=5.8 Hz), 128.3, 127.9, 127.6(t, J=11.5 Hz), 127.0, 126.3, 116.8 (t, J=20.7 Hz), 106.5 (t, J=4.6 Hz),32.8 (t, J=4.6 Hz), 31.1 (t, J=9.2 Hz).

³¹P{¹H} NMR (CD₂Cl₂): δ −7.3.

A representation of the molecular structure of complex 27 is shown inFIG. 3.

Experimental—Polymerizations:

In the following experiments pressure is reported in atmospheres andpounds per square inch. The conversion factors to S. I. Units are; 1 psiequals 6.894757 kPa and 1 atm equals 101.325 kPa.

Transition metal compound or complex (TMC) solutions were typicallyprepared using toluene (ExxonMobil Chemical—anhydrous, stored under N₂)(98%). Unless otherwise mentioned, TMC solutions are 0.2 mmol/L for C₂and C₂/C₈ (co)polymerizations.

Solvents, polymerization grade toluene and hexanes were supplied byExxonMobil Chemical Co. and thoroughly dried and degassed prior to use.

1-octene (98%) was purchased from Aldrich Chemical Company and dried bystirring over NaK overnight followed by filtration through basic alumina(Aldrich Chemical Company, Brockman Basic 1).

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 500 cc Oxyclear cylinder from Labclear(Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å molesieves purchased from Aldrich Chemical Company, and a 500 cc columnpacked with dried 5 Å mole sieves purchased from Aldrich ChemicalCompany.

MAO (methylalumoxane, 10 wt % in toluene) was purchased from AlbemarleCorporation and was used as a 1 wt % or 2 wt % in toluene solution.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N₂) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8runs), septum inlets, regulated supply of nitrogen, ethylene andpropylene, and equipped with disposable PEEK mechanical stirrers (800RPM). The autoclaves were prepared by purging with dry nitrogen at 110°C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Ethylene Polymerization or Ethylene/1-octene Copolymerization:

The reactor was prepared as described above, and then purged withethylene. Toluene, 1-octene, and MAO, were added via syringe at roomtemperature and atmospheric pressure. The reactor was then brought toprocess temperature (80° C.) and charged with ethylene to processpressure (75 psig =517.1 kPa) while stirring at 800 RPM. The TMC (0.02μmol) was added via syringe with the reactor at process conditions.Amounts of reagents not specified above are given in Tables 2 and 4.Ethylene was allowed to enter (through the use of computer controlledsolenoid valves) the autoclaves during polymerization to maintainreactor gauge pressure (+/−2 psig). Reactor temperature was monitoredand typically maintained within +/−1° C. Polymerizations were halted byaddition of approximately 50 psid O₂/Ar (5 mole % O₂) gas mixture to theautoclaves for approximately 30 seconds. The polymerizations werequenched after a predetermined cumulative amount of ethylene had beenadded or for a maximum of 20 minutes polymerization time. The finalconversion (in psi) of ethylene added/consumed is reported in the Tables2 and 4, in addition to the quench time for each run. The reactors werecooled and vented. The polymer was isolated after the solvent wasremoved in-vacuo. Yields reported include total weight of polymer andresidual catalyst. Catalyst activity is reported as grams of polymer permmol transition metal compound per atmosphere ethylene per hour ofreaction time (g/mmol·hr·atm).

Polymer Characterization:

Polymer characterization results for polyethylene samples are reportedin Table 3, and for ethylene-1-octene copolymers are reported in Table5.

For analytical testing, polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%from Aldrich) at 160° C. in a shaker oven for approximately 3 hours. Thetypical concentration of polymer in solution is between 0.4 to 0.9 mg/mLwith a BHT concentration of 1.25 mg BHT/mL of TCB. Samples are cooled to135° C. for testing.

Molecular weights (weight average molecular weight (Mw) and numberaverage molecular weight (Mn)) and molecular weight distribution(MWD=Mw/Mn), which is also sometimes referred to as the polydispersity(PDI) of the polymer, were measured by Gel Permeation Chromatographyusing a Symyx Technology GPC equipped with evaporative light scatteringdetector and calibrated using polystyrene standards (PolymerLaboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between5000 and 3,390,000). Samples were run in TCB at (135° C. sampletemperatures, 160° C. oven/columns) using three Polymer Laboratories:PLgel 10 μm Mixed-B 300×7.5 mm columns in series. No column spreadingcorrections were employed. Numerical analyses were performed usingEpoch® software available from Symyx Technologies.

The sample preparation for SAMMS (Sensory Array Modular MeasurementSystem) thermal analysis measurements involved depositing the stabilizedpolymer solution onto a silanized wafer (Part Number S10457, Symyx). Thesolvent was then evaporated off at ˜145° C. By this method,approximately between 0.12 and 0.24 mg of polymer is deposited onto eachcorresponding wafer cell. Thermal analysis was measured on a SymyxTechnologies SAMMS instrument that measures polymer melt temperaturesvia the 3 ω technique. The analysis first employs a rapid-scan protocolthat heats each cell from 27° C. to 200° C. in ˜35 seconds and thenrapidly cools the sample to room temperature. This complete proceduretakes approximately 60 seconds per cell and is used to minimize eachsample's thermal history. The second step involves running ahigh-resolution scan protocol to measure the second melt of the sample.The protocol heats each cell from 27° C. to 200° C. in ˜3 minutes andthen rapidly cools the sample to room temperature. The high-resolutionscan takes approximately three times the amount of time to complete asthe rapid-scan protocol. If multiple melting peaks are present, Epoch®Software reports the largest amplitude peak. SAMMS data is reportedunder the heading of Tm (C) in Tables 3 and 5.

Samples for infrared analysis were prepared by depositing the stabilizedpolymer solution onto a silanized wafer (Part number S10860, Symyx). Bythis method, approximately between 0.12 and 0.24 mg of polymer isdeposited on the wafer cell. The samples were subsequently analyzed on aBrucker Equinox 55 FTIR spectrometer equipped with Pikes's MappIRspecular reflectance sample accessory. Spectra, covering a spectralrange of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolutionwith 32 scans.

For ethylene-1-octene copolymers, the wt. % copolymer is determined viameasurement of the methyl deformation band at ˜1375 cm⁻¹. The peakheight of this band is normalized by the combination and overtone bandat ˜4321 cm⁻¹, which corrects for path length differences. Thenormalized peak height is correlated to individual calibration curvesfrom ¹H NMR data to predict the wt. % copolymer content within aconcentration range of ˜2 to 35 wt. % for octene. Typically, R²correlations of 0.98 or greater are achieved. These numbers are reportedin Table 5 under the heading, Octene wt %). TABLE 2 EthylenePolymerization Runs - Part 1. Total Final Quench Activator TolueneConversion Time Polymer Activity Ex# TMC (μmol) (mL) (psi) (sec) Yield(g) (g/mmol · hr · atm) PE-25 25 9.98 3.80 25.5 52.0 0.087 59,038 PE-2625 9.98 3.80 25.2 43.2 0.082 66,982 PE-27 25 9.98 3.80 25.5 48.0 0.08159,585 PE-28 25 9.98 3.80 25.6 48.4 0.094 68,505

TABLE 3 Ethylene Polymerization Runs - Part 2. Tm Ex# TMC Mw Mn PDI (°C.) PE-25 25 6,568 4,513 1.5 none PE-26 25 6,708 4,633 1.4 none PE-27 255,357 3,684 1.5 none PE-28 25 6,896 4,828 1.4 130.2

TABLE 4 Ethylene-1-Octene Polymerization Runs - Part 1. Total FinalQuench Activator 1-Octene Toluene Conversion Time Polymer Activity Ex#TMC (μmol) (μmol) (mL) (psi) (sec) Yield (g) (g/mmol · hr · atm) EO-2625 9.98 638.1 3.80 25.0 41.3 0.091 77,792 EO-27 25 9.98 638.1 3.80 25.542.9 0.091 74,749 EO-28 25 9.98 638.1 3.80 25.0 66.4 0.103 54,718

TABLE 5 Ethylene-1-Octene Polymerization Runs - Part 2. Octene Tm Ex#TMC Mw Mn PDI (wt %) (° C.) EO-26 25 6,707 4,614 1.5 7.5 102.3 EO-27 255,358 3,707 1.4 4.7 90.8 EO-28 25 6,645 4,572 1.5 11.7 123.6

While certain representative embodiments and details have been shown toillustrate the invention, it will be apparent to skilled artisans thatvarious process and product changes from those disclosed in thisapplication may be made without departing from this invention's scope,which the appended claims define.

All cited patents, test procedures, priority documents, and other citeddocuments are fully incorporated by reference to the extent that thismaterial is consistent with this specification and for all jurisdictionsin which such incorporation is permitted.

Certain features of the present invention are described in terms of aset of numerical upper limits and a set of numerical lower limits. Thisspecification discloses all ranges formed by any combination of theselimits. All combinations of these limits are within the scope of theinvention unless otherwise indicated.

1. A metallocene compound represented by formula:

wherein M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; E is a substituted or unsubstitutedindenyl ligand that is bonded to Y through the two position of theindenyl ring; A is bonded to Y, and is a substituted or unsubstitutedcyclopentadienyl ligand, a substituted or unsubstitutedheterocyclopentadienyl ligand, a substituted or unsubstituted indenylligand, a substituted or unsubstituted heteroindenyl ligand, asubstituted or unsubstituted fluorenyl ligand, a substituted orunsubstituted heterofluorenyl ligand, or other mono-anionic ligand, or Amay, independently, be defined as E; Y is a phosphorus containing groupthat is bonded to both E and A, and is bonded via the phosphorus atom toE; and each X is, independently, a univalent anionic ligand, or both Xare joined and bound to the metal atom to form a metallocycle ring, orboth X join to form a chelating ligand, a diene ligand, or an alkylideneligand.
 2. The compound of claim 1 wherein M is Ti, Zr or Hf.
 3. Thecompound of claim 1 wherein Y is selected from the group of diradicalsconsisting of PR, RP—PR, RN—PR, where each R is, independently, selectedfrom the group consisting of C1 to C30 hydrocarbyls.
 4. The compound ofclaim 1 wherein Y is selected from the group of diradicals consisting ofPR, RP—PR, RN—PR, where each R is, independently, selected from thegroup consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, phenyl, cyclohexyl, tolyl,mesityl, naphthyl, and all isomers thereof.
 5. The compound of claim 1wherein each X is, independently, selected from the group consisting ofchloride, bromide, fluoride, iodide, hydride, and C1 to C30hydrocarbyls.
 6. The compound of claim 1 wherein each X is,independently, selected from the group consisting of chloride, bromide,fluoride, iodide, hydride, methyl, ethyl, propyl, butyl, pentyl, hexyl,phenyl, benzyl, and all isomers thereof.
 7. The compound of claim 1wherein two X together are selected from butadiene, methylbutadiene,pentadiene, methylpentadiene, dimethylpentadiene, hexadiene,methylhexadiene, dimethylhexadiene, methylidene, ethylidene,propylidene, propandiyl, butandiyl, pentandiyl, and hexandiyl.
 8. Thecompound of claim 1 wherein A is selected from the group consisting ofindenyl, methylindenyl, dimethylindenyl, methylphenylindenyl,methyltolylindenyl, methyl(dipropylphenyl)indenyl,methyl(dimethylphenyl)indenyl methylnaphthylindenyl, tetrahydroindenyl,fluorenyl, octahydrofluorenyl, dibutylfluorenyl, cyclopentadienyl,methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl,butylcyclopentadienyl, methylpropylcyclopentadienyl,methylbutylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
 9. Ametallocene compounds represented by formula:

where: M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; each R¹, R², R³, R⁴, R⁵, and R⁶ is,independently, a hydrogen, or a hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, or substituted germylcarbyl substituent, andoptionally, adjacent R¹, R², R³, R⁴, R⁵, and R⁶ groups may join togetherto form a substituted or unsubstituted, saturated, partiallyunsaturated, or aromatic cyclic or polycyclic substituent; A is asubstituted or unsubstituted cyclopentadienyl ligand, a substituted orunsubstituted heterocyclopentadienyl ligand, a substituted orunsubstituted indenyl ligand, a substituted or unsubstitutedheteroindenyl ligand, a substituted or unsubstituted fluorenyl ligand,or a substituted or unsubstituted heterofluorenyl ligand where A isbonded to Y through any bondable ring position; or A is a mono-anionicligand such as a substituted or unsubstituted pentadienyl ligand, asubstituted or unsubstituted allyl ligand, or a substituted orunsubstituted boratabenzene ligand; and Y is PR, RP—PR, or RN—PR, whereeach R is, independently, a hydrocarbyl, substituted hydrocarbyl,halocarbyl, or substituted halocarbyl substituent, and optionally,adjacent R groups may join together to form a substituted orunsubstituted, saturated or partially unsaturated cyclic or polycyclicsubstituent; and X are, independently, hydride radicals, hydrocarbylradicals, substituted hydrocarbyl radicals, halocarbyl radicals,substituted halocarbyl radicals, silylcarbyl radicals, substitutedsilylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbylradicals; or both X are joined and bound to the metal atom to form ametallacycle ring containing from about 3 to about 20 carbon atoms; orboth together can be an olefin, diolefin or aryne ligand; or both X may,independently, be a halogen, alkoxide, aryloxide, amide, phosphide orother univalent anionic ligand or both X can also be joined to form aanionic chelating ligand.
 10. The compound of claim 9 wherein M is Ti,Zr or Hf.
 11. The compound of claim 9 wherein Y is selected from thegroup of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of C1 to C30hydrocarbyls.
 12. The compound of claim 9 wherein Y is selected from thegroup of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, phenyl, cyclohexyl, tolyl, mesityl, naphthyl, and all isomersthereof.
 13. The compound of claim 9 wherein each X is, independently,selected from the group consisting of chloride, bromide, fluoride,iodide, hydride, and C1 to C30 hydrocarbyls.
 14. The compound of claim 9wherein each X is, independently, selected from the group consisting ofchloride, bromide, fluoride, iodide, hydride, methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, benzyl, and all isomers thereof,
 15. Thecompound of claim 9 wherein two X together are selected from butadiene,methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene,hexadiene, methylhexadiene, dimethylhexadiene, methylidene, ethylidene,propylidene, propandiyl, butandiyl, pentandiyl, and hexandiyl.
 16. Thecompound of claim 9 wherein A is selected from the group consisting ofindenyl, methylindenyl, dimethylindenyl, methylphenylindenyl,methyltolylindenyl, methyl(dipropylphenyl)indenyl,methyl(dimethylphenyl)indenyl methylnaphthylindenyl, tetrahydroindenyl,fluorenyl, octahydrofluorenyl, dibutylfluorenyl, cyclopentadienyl,methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl,butylcyclopentadienyl, methylpropylcyclopentadienyl,methylbutylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
 17. Thecompound of claim 9 wherein each R¹, R², R³, R⁴, R⁵, and R⁶ is,independently, selected from hydrogen or from the group consisting of C1to C30 hydrocarbyls.
 18. The compound of claim 9 wherein each R¹, R²,R³, R⁴, R⁵, and R⁶ is, independently, selected from from hydrogen orfrom the group consisting of methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl,cyclohexyl, tolyl, mesityl, naphthyl, and all isomers thereof.
 19. Acompound represented by the formula:

where: M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹, and R¹² is, independently, hydrogen, or a hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,silylcarbyl, substituted silylcarbyl, germylcarbyl, or substitutedgermylcarbyl substituent, and optionally, adjacent R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² substituents may join together to forma substituted or unsubstituted, saturated, partially unsaturated, oraromatic cyclic or polycyclic substituent; Y is PR, RP—PR, or RN—PR,where each R is, independently, a hydrocarbyl, substituted hydrocarbyl,halocarbyl, or substituted halocarbyl substituent, and optionally,adjacent R groups may join together to form a substituted orunsubstituted, saturated or partially unsaturated cyclic or polycyclicsubstituent; and X are, independently, hydride radicals, hydrocarbylradicals, substituted hydrocarbyl radicals, halocarbyl radicals,substituted halocarbyl radicals, silylcarbyl radicals, substitutedsilylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbylradicals; or both X are joined and bound to the metal atom to form ametallacycle ring containing from about 3 to about 20 carbon atoms; orboth together can be an olefin, diolefin or aryne ligand; or each X may,independently, be a halogen, alkoxide, aryloxide, amide, phosphide orother univalent anionic ligand or both X can also be joined to form aanionic chelating ligand.
 20. The compound of claim 19 wherein M is Ti,Zr or Hf.
 21. The compound of claim 19 wherein Y is selected from thegroup of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of C1 to C30hydrocarbyls.
 22. The compound of claim 19 wherein Y is selected fromthe group of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, phenyl, cyclohexyl, tolyl, mesityl, naphthyl, and all isomersthereof.
 23. The compound of claim 19 wherein each X is, independently,selected from the group consisting of chloride, bromide, fluoride,iodide, hydride, and C1 to C30 hydrocarbyls.
 24. The compound of claim19 wherein each X is, independently, selected from the group consistingof chloride, bromide, fluoride, iodide, hydride, methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, benzyl, and all isomers thereof,
 25. Thecompound of claim 19 wherein two X together are selected from butadiene,methylbutadiene, pentadiene, methylpentadiene, dimethylpentadiene,hexadiene, methylhexadiene, dimethylhexadiene, methylidene, ethylidene,propylidene, propandiyl, butandiyl, pentandiyl, and hexandiyl.
 26. Thecompound of claim 19 wherein A is selected from the group consisting ofindenyl, methylindenyl, dimethylindenyl, methylphenylindenyl,methyltolylindenyl, methyl(dipropylphenyl)indenyl,methyl(dimethylphenyl)indenyl methylnaphthylindenyl, tetrahydroindenyl,fluorenyl, octahydrofluorenyl, dibutylfluorenyl, cyclopentadienyl,methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl,butylcyclopentadienyl, methylpropylcyclopentadienyl,methylbutylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
 27. Thecompound of claim 19 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, and R¹² is, independently, selected from hydrogen or from thegroup consisting of C1 to C30 hydrocarbyls.
 28. The compound of claim 19wherein each R¹, R², R³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is,independently, selected from hydrogen or from the group consisting ofmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, phenyl, cyclohexyl, tolyl, mesityl, naphthyl,and all isomers thereof.
 29. The compound claim 9 wherein: 1) each R¹,R², R³, R⁴, R⁵, and R⁶ is, independently, selected from hydrogen or fromthe group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, cyclohexyl,tolyl, mesityl, naphthyl, and all isomers thereof; 2) Y is selected fromthe group of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, phenyl, cyclohexyl, tolyl, mesityl, naphthyl, and all isomersthereof; 3) X is, independently, selected from the group consisting ofchloride, bromide, fluoride, iodide, hydride, methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, benzyl, and all isomers thereof; 4) M isTi, Zr, or Hf; and 5) A is selected from the group consisting ofindenyl, methylindenyl, dimethylindenyl, methylphenylindenyl,methyltolylindenyl, methyl(dipropylphenyl)indenyl,methyl(dimethylphenyl)indenyl methylnaphthylindenyl, tetrahydroindenyl,fluorenyl, octahydrofluorenyl, dibutylfluorenyl, cyclopentadienyl,methylcyclopentadienyl, ethylcyclopentadienyl, propylcyclopentadienyl,butylcyclopentadienyl, methylpropylcyclopentadienyl,methylbutylcyclopentadienyl, dimethylcyclopentadienyl,trimethylcyclopentadienyl, and tetramethylcyclopentadienyl.
 30. Thecompound claim 19 wherein: 1) each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, and R¹² is, independently, selected from hydrogen or from thegroup consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, phenyl, cyclohexyl, tolyl,mesityl, naphthyl, and all isomers thereof; 2) Y is selected from thegroup of diradicals consisting of PR, RP—PR, RN—PR, where each R is,independently, selected from the group consisting of methyl, ethyl,propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, phenyl, cyclohexyl, tolyl, mesityl, naphthyl, and all isomersthereof; 3) X is, independently, selected from the group consisting ofchloride, bromide, fluoride, iodide, hydride, methyl, ethyl, propyl,butyl, pentyl, hexyl, phenyl, benzyl, and all isomers thereof; and 4) Mis Ti, Zr, or Hf;
 31. A compound selected from the group consisting of:2,2′-phenylphosphindiyl-bis(indenyl)zirconium dichloride,2,2′-methylphosphindiyl-bis(indenyl)zirconium dichloride,2,2′-ethylphosphindiyl-bis(indenyl)zirconium dichloride,2,2′-propylphosphindiyl-bis(indenyl)zirconium dichloride,2,2′-butylphosphindiyl-bis(indenyl)zirconium dichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dichloride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dichloride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dichloride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dichloride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dichloride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dichloride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconiumdichloride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdichloride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdichloride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdichloride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdichloride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconiumdichloride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconiumdichloride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconiumdichloride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconiumdichloride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconiumdichloride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconiumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconiumdichloride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdichloride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdichloride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdichloride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdichloride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconiumdichloride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconiumdichloride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdichloride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdichloride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconiumdichloride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconiumdichloride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconiumdichloride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconiumdichloride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconiumdichloride,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconiumdichloride, 2,2′-phenylphosphindiyl-bis(indenyl)zirconium dimethyl,2,2′-methylphosphindiyl-bis(indenyl)zirconium dimethyl,2,2′-ethylphosphindiyl-bis(indenyl)zirconium dimethyl,2,2′-propylphosphindiyl-bis(indenyl)zirconium dimethyl,2,2′-butylphosphindiyl-bis(indenyl)zirconium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dimethyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dimethyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconiumdimethyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdimethyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdimethyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdimethyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdimethyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdimethyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconiumdimethyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconiumdimethyl, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconiumdimethyl, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconiumdimethyl, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdimethyl, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdimethyl, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdimethyl, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdimethyl, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconiumdimethyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconiumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdimethyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium dimethyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium dimethyl,2,2′-phenylphosphindiyl-bis(indenyl)zirconium dibenzyl,2,2′-methylphosphindiyl-bis(indenyl)zirconium dibenzyl,2,2′-ethylphosphindiyl-bis(indenyl)zirconium dibenzyl,2,2′-propylphosphindiyl-bis(indenyl)zirconium dibenzyl,2,2′-butylphosphindiyl-bis(indenyl)zirconium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dibenzyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium dibenzyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconiumdibenzyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdibenzyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdibenzyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdibenzyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdibenzyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconiumdibenzyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconiumdibenzyl, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconiumdibenzyl, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconiumdibenzyl, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdibenzyl, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdibenzyl, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdibenzyl, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdibenzyl, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconiumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconiumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdibenzyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconium dibenzyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconium dibenzyl,2,2′-phenylphosphindiyl-bis(indenyl)zirconium difluoride,2,2′-methylphosphindiyl-bis(indenyl)zirconium difluoride,2,2′-ethylphosphindiyl-bis(indenyl)zirconium difluoride,2,2′-propylphosphindiyl-bis(indenyl)zirconium difluoride,2,2′-butylphosphindiyl-bis(indenyl)zirconium difluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium difluoride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)zirconium difluoride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)zirconium difluoride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)zirconium difluoride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)zirconium difluoride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)zirconium difluoride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)zirconiumdifluoride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdifluoride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdifluoride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdifluoride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdifluoride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)zirconiumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)zirconiumdifluoride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)zirconiumdifluoride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)zirconiumdifluoride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)zirconiumdifluoride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)zirconiumdifluoride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)zirconiumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)zirconiumdifluoride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdifluoride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdifluoride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdifluoride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdifluoride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)zirconiumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)zirconiumdifluoride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)zirconiumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)zirconiumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)zirconiumdifluoride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)zirconiumdifluoride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)zirconiumdifluoride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)zirconiumdifluoride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)zirconiumdifluoride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)zirconiumdifluoride,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)zirconiumdifluoride, 2,1′-phenylphosphindiyl-bis(indenyl)zirconium dichloride,2,1′-methylphosphindiyl-bis(indenyl)zirconium dichloride,2,1′-ethylphosphindiyl-bis(indenyl)zirconium dichloride,2,1′-propylphosphindiyl-bis(indenyl)zirconium dichloride,2,1′-butylphosphindiyl-bis(indenyl)zirconium dichloride,2,1′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)zirconium dichloride,2,2′-phenylphosphindiyl-bis(indenyl)hafnium dichloride,2,2′-methylphosphindiyl-bis(indenyl)hafnium dichloride,2,2′-ethylphosphindiyl-bis(indenyl)hafnium dichloride,2,2′-propylphosphindiyl-bis(indenyl)hafnium dichloride,2,2′-butylphosphindiyl-bis(indenyl)hafnium dichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dichloride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dichloride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafniumdichloride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdichloride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdichloride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdichloride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdichloride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafniumdichloride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafniumdichloride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafniumdichloride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafniumdichloride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafniumdichloride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafniumdichloride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdichloride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdichloride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdichloride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdichloride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafniumdichloride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafniumdichloride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdichloride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdichloride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafniumdichloride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafniumdichloride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafniumdichloride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafniumdichloride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafniumdichloride, 2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafniumdichloride, 2,2′-phenylphosphindiyl-bis(indenyl)hafnium dimethyl,2,2′-methylphosphindiyl-bis(indenyl)hafnium dimethyl,2,2′-ethylphosphindiyl-bis(indenyl)hafnium dimethyl,2,2′-propylphosphindiyl-bis(indenyl)hafnium dimethyl,2,2′-butylphosphindiyl-bis(indenyl)hafnium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dimethyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dimethyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafniumdimethyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdimethyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdimethyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdimethyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdimethyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdimethyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafniumdimethyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium dimethyl,2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdimethyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium dimethyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium dimethyl,2,2′-phenylphosphindiyl-bis(indenyl)hafnium dibenzyl,2,2′-methylphosphindiyl-bis(indenyl)hafnium dibenzyl,2,2′-ethylphosphindiyl-bis(indenyl)hafnium dibenzyl,2,2′-propylphosphindiyl-bis(indenyl)hafnium dibenzyl,2,2′-butylphosphindiyl-bis(indenyl)hafnium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium dibenzyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium dibenzyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafniumdibenzyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdibenzyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdibenzyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdibenzyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdibenzyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafniumdibenzyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafnium dibenzyl,2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafnium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdibenzyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafnium dibenzyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafnium dibenzyl,2,2′-phenylphosphindiyl-bis(indenyl)hafnium difluoride,2,2′-methylphosphindiyl-bis(indenyl)hafnium difluoride,2,2′-ethylphosphindiyl-bis(indenyl)hafnium difluoride,2,2′-propylphosphindiyl-bis(indenyl)hafnium difluoride,2,2′-butylphosphindiyl-bis(indenyl)hafnium difluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)hafnium difluoride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)hafnium difluoride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)hafniumdifluoride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdifluoride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdifluoride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdifluoride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdifluoride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)hafniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)hafniumdifluoride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)hafniumdifluoride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)hafniumdifluoride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)hafniumdifluoride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)hafniumdifluoride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)hafniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)hafniumdifluoride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdifluoride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdifluoride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdifluoride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdifluoride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)hafniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)hafniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)hafniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)hafniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)hafniumdifluoride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)hafniumdifluoride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)hafniumdifluoride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)hafniumdifluoride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)hafniumdifluoride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)hafniumdifluoride, 2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)hafniumdifluoride, 2,2′-phenylphosphindiyl-bis(indenyl)titanium dichloride,2,2′-methylphosphindiyl-bis(indenyl)titanium dichloride,2,2′-ethylphosphindiyl-bis(indenyl)titanium dichloride,2,2′-propylphosphindiyl-bis(indenyl)titanium dichloride,2,2′-butylphosphindiyl-bis(indenyl)titanium dichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dichloride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium dichloride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium dichloride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium dichloride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium dichloride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium dichloride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titaniumdichloride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdichloride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdichloride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdichloride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdichloride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titaniumdichloride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titaniumdichloride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)titaniumdichloride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titaniumdichloride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)titaniumdichloride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)titaniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titaniumdichloride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdichloride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdichloride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdichloride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdichloride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdichloride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titaniumdichloride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titaniumdichloride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdichloride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdichloride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titaniumdichloride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)titaniumdichloride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titaniumdichloride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)titaniumdichloride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)titaniumdichloride,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titaniumdichloride, 2,2′-phenylphosphindiyl-bis(indenyl)titanium dimethyl,2,2′-methylphosphindiyl-bis(indenyl)titanium dimethyl,2,2′-ethylphosphindiyl-bis(indenyl)titanium dimethyl,2,2′-propylphosphindiyl-bis(indenyl)titanium dimethyl,2,2′-butylphosphindiyl-bis(indenyl)titanium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dimethyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium dimethyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titaniumdimethyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdimethyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdimethyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdimethyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdimethyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdimethyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titaniumdimethyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium dimethyl,2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium dimethyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titaniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titaniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdimethyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdimethyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium dimethyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium dimethyl,2,2′-phenylphosphindiyl-bis(indenyl)titanium dibenzyl,2,2′-methylphosphindiyl-bis(indenyl)titanium dibenzyl,2,2′-ethylphosphindiyl-bis(indenyl)titanium dibenzyl,2,2′-propylphosphindiyl-bis(indenyl)titanium dibenzyl,2,2′-butylphosphindiyl-bis(indenyl)titanium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium dibenzyl,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium dibenzyl,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titaniumdibenzyl, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdibenzyl, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdibenzyl, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdibenzyl, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdibenzyl, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titaniumdibenzyl, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,2,2′-methylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,2,2′-propylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,2,2′-butylphosphindiyl-bis(4-phenylindenyl)titanium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titanium dibenzyl,2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titanium dibenzyl,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titaniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titaniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdibenzyl,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdibenzyl, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,2,9′-methylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,2,9′-propylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,2,9′-butylphosphindiyl(indenyl)(fluorenyl)titanium dibenzyl,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titanium dibenzyl,2,2′-phenylphosphindiyl-bis(indenyl)titanium difluoride,2,2′-methylphosphindiyl-bis(indenyl)titanium difluoride,2,2′-ethylphosphindiyl-bis(indenyl)titanium difluoride,2,2′-propylphosphindiyl-bis(indenyl)titanium difluoride,2,2′-butylphosphindiyl-bis(indenyl)titanium difluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(indenyl)titanium difluoride,2,1′-phenylphosphindiyl(indenyl)(cyclopentadienyl)titanium difluoride,2,1′-methylphosphindiyl(indenyl)(cyclopentadienyl)titanium difluoride,2,1′-ethylphosphindiyl(indenyl)(cyclopentadienyl)titanium difluoride,2,1′-propylphosphindiyl(indenyl)(cyclopentadienyl)titanium difluoride,2,1′-butylphosphindiyl(indenyl)(cyclopentadienyl)titanium difluoride,2,1′-1,2-dimethyldiphosphandiyl)(indenyl)(cyclopentadienyl)titaniumdifluoride, 2,2′-phenylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdifluoride, 2,2′-methylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdifluoride, 2,2′-ethylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdifluoride, 2,2′-propylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdifluoride, 2,2′-butylphosphindiyl(indenyl)(tetrahydroindenyl)titaniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)(indenyl)(tetrahydroindenyl)titaniumdifluoride, 2,2′-phenylphosphindiyl-bis(4-phenylindenyl)titaniumdifluoride, 2,2′-methylphosphindiyl-bis(4-phenylindenyl)titaniumdifluoride, 2,2′-ethylphosphindiyl-bis(4-phenylindenyl)titaniumdifluoride, 2,2′-propylphosphindiyl-bis(4-phenylindenyl)titaniumdifluoride, 2,2′-butylphosphindiyl-bis(4-phenylindenyl)titaniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4-phenylindenyl)titaniumdifluoride, 2,2′-phenylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdifluoride, 2,2′-methylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdifluoride, 2,2′-ethylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdifluoride, 2,2′-propylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdifluoride, 2,2′-butylphosphindiyl-bis(4,7-dimethylindenyl)titaniumdifluoride,2,2′-(1,2-dimethyldiphosphandiyl)-bis(4,7-dimethylindenyl)titaniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-methylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-propylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-butylphosphindiyl(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(3-methylcyclopentadienyl)titaniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-methylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-propylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-butylphosphindiyl(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2,4-dimethylcyclopentadienyl)titaniumdifluoride,2,1′-phenylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride,2,1′-methylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride,2,1′-ethylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride,2,1′-propylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride,2,1′-butylphosphindiyl(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride,2,1′-(1,2-dimethyldiphosphandiyl)(indenyl)(2-methyl-4-butylcyclopentadienyl)titaniumdifluoride, 2,9′-phenylphosphindiyl(indenyl)(fluorenyl)titaniumdifluoride, 2,9′-methylphosphindiyl(indenyl)(fluorenyl)titaniumdifluoride, 2,9′-ethylphosphindiyl(indenyl)(fluorenyl)titaniumdifluoride, 2,9′-propylphosphindiyl(indenyl)(fluorenyl)titaniumdifluoride, 2,9′-butylphosphindiyl(indenyl)(fluorenyl)titaniumdifluoride,2,9′-(1,2-dimethyldiphosphandiyl)(indenyl)(fluorenyl)titaniumdifluoride, and the like.
 32. A catalyst system comprising an activatorand the compound of claim
 1. 33. The catalyst system of claim 32 whereinthe activator comprises an alumoxane.
 34. The catalyst system of claim32 wherein the activator comprises a non-coordinating anion.
 35. Thecatalyst system of claim 32 wherein the activator is selected from thegroup consisting of trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tropillium tetraphenylborate,triphenylcarbenium tetraphenylborate, triphenylphosphoniumtetraphenylborate, triethylsilylium tetraphenylborate,benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 36. The catalyst systemof claim 32 wherein the activator is selected from the group consistingof N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbeniumtetra(perfluorophenyl)borate.
 37. A catalyst system comprising anactivator and the compound of claim
 9. 38. The catalyst system of claim37 wherein the activator comprises an alumoxane.
 39. The catalyst systemof claim 37 wherein the activator comprises a non-coordinating anion.40. The catalyst system of claim 37 wherein the activator is selectedfrom the group consisting of trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tropillium tetraphenylborate,triphenylcarbenium tetraphenylborate, triphenylphosphoniumtetraphenylborate, triethylsilylium tetraphenylborate,benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 41. The catalyst systemof claim 9 wherein the activator is selected from the group consistingof N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbeniumtetra(perfluorophenyl)borate.
 42. A catalyst system comprising anactivator and the compound of claim
 19. 43. The catalyst system of claim42 wherein the activator comprises an alumoxane.
 44. The catalyst systemof claim 42 wherein the activator comprises a non-coordinating anion.45. The catalyst system of claim 42 wherein the activator is selectedfrom the group consisting of trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tropillium tetraphenylborate,triphenylcarbenium tetraphenylborate, triphenylphosphoniumtetraphenylborate, triethylsilylium tetraphenylborate,benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 46. The catalyst systemof claim 42 wherein the activator is selected from the group consistingof N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbeniumtetra(perfluorophenyl)borate.
 47. A catalyst system comprising thecatalyst compound of claim 31 and an activator.
 48. The catalyst systemof claim 47 wherein the activator comprises an alumoxane.
 49. Thecatalyst system of claim 47 wherein the activator is selected from thegroup consisting of trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(tert-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(tert-butyl)ammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(iso-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tropillium tetraphenylborate,triphenylcarbenium tetraphenylborate, triphenylphosphoniumtetraphenylborate, triethylsilylium tetraphenylborate,benzene(diazonium)tetraphenylborate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, benzene(diazonium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.
 50. A catalyst systemcomprisng the compound of claim 31 and an activator selected from thegroup consisting of N,N-dimethylaniliniumtetrakis(perfluorophenyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbeniumtetra(perfluorophenyl)borate.
 51. A method to polymerize unsaturatedmonomers comprising contacting the catalyst system of claim 32 withunsaturated monomers.
 52. The method of claim 51 wherein the monomerscomprise ethylene.
 53. The method of claim 51 wherein the monomerscomprise propylene.
 54. The method of claim 51 wherein the monomerscomprise ethylene and or propylene and one or more comonomers selectedfrom the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene,1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene,1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene,1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene,1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane,vinylnorbornane, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norboenadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,1,5-diallylcyclooctane, styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, divinylbenzene,1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene,6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene,1,9-decadiene, 1,11-dodecene, 1,13-tetradecene and9-methyl-1,9-decadiene.
 55. A method to polymerize unsaturated monomerscomprising contacting the catalyst system of claim 37 with unsaturatedmonomers.
 56. The method of claim 55 wherein the monomers compriseethylene.
 57. The method of claim 55 wherein the monomers comprisepropylene.
 58. The method of claim 55 wherein the monomers compriseethylene and or propylene and one or more comonomers selected from thegroup consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene,1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane,vinylnorbornane, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,1,5-diallylcyclooctane, styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, divinylbenzene,1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene,6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene,1,9-decadiene, 1,11-dodecene, 1,13-tetradecene and9-methyl-1,9-decadiene.
 59. A method to polymerize unsaturated monomerscomprising contacting the catalyst system of claim 42 with unsaturatedmonomers.
 60. The method of claim 59 wherein the monomers compriseethylene.
 61. The method of claim 59 wherein the monomers comprisepropylene.
 62. The method of claim 59 wherein the monomers compriseethylene and or propylene and one or more comonomers selected from thegroup consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene,I-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene,1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane,vinylnorbornane, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,1,5-diallylcyclooctane, styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, divinylbenzene,1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene,6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene,1,9-decadiene, 1,11-dodecene, 1,13-tetradecene and9-methyl-1,9-decadiene.
 63. A method to polymerize unsaturated monomerscomprising contacting the catalyst system of claim 49 with unsaturatedmonomers.
 64. The method of claim 63 wherein the monomers compriseethylene.
 65. The method of claim 63 wherein the monomers comprisepropylene.
 66. The method of claim 63 wherein the monomers compriseethylene and or propylene and one or more comonomers selected from thegroup consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene,1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene,1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene,5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane,vinylnorbornane, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,1,5-diallylcyclooctane, styrene, para-methylstyrene,para-t-butylstyrene, vinylnaphthylene, vinyltoluene, divinylbenzene,1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene,6-methyl-1,6-heptadiene, 1,7-octadiene, 7-methyl-1,7-octadiene,1,9-decadiene, 1,11-dodecene, 1,1 3-tetradecene and9-methyl-1,9-decadiene.